1-(3-heterocyclylphenyl)-s-triazine-2,4,6-oxo or thiortione herbicidal agents

ABSTRACT

There is provided a 1-(3-heterocyclylphenyl)-s-triazine-2,4,6-oxo or thiotrione compound having the structural formula I ##STR1## Further provided are a composition and a method comprising that compound for the control of undesirable plant species.

BACKGROUND OF THE INVENTION

Weeds cause tremendous global economic losses by reducing crop yieldsand lowering crop quality. In the United States alone, agronomic cropsmust compete with hundreds of weed species.

In spite of the commercial herbicides available today, damage to cropscaused by weeds still occurs. Accordingly, there is ongoing research tocreate new and more effective herbicides.

Certain heterocyclylphenyl herbicidal agents are known (see, e.g., WO85/01939, EP 77938-A2 and U.S. Pat. No. 5,356,863). However, none ofthose publications disclose heterocyclylphenyl compounds which aresubstituted with a 1,3,5-triazine-2,4,6-trione group.

Fungicidal 1,3,5-triazine-2,4,6-triones are described in U.S. Pat. No.4,876,253 and U.S. Pat. No. 4,927,824. However, those patents do notdisclose any heterocyclylphenyl substituted1,3,5-triazine-2,4,6-triones. Further, the patentees do not disclose anyherbicidal utility for their compounds.

EP 640600-A1 and U.S. Pat. No. 4,512,797 disclose herbicidal1,3,5-triazine-2,4,6-triones. However, those publications do notdisclose any heterocyclylphenyl substituted 1,3,5-triazine-2,4,6-trionecompounds.

It is an object of the present invention to provide compounds which arehighly effective for controlling undesirable plant species.

It is also an object of the present invention to provide methods forcontrolling undesirable plant species.

Those and other objects of the present invention will become moreapparent from the detailed description thereof set forth below.

SUMMARY OF THE INVENTION

The present invention describes1-(3-heterocyclylphenyl)-s-triazine-2,4,6-oxo or thiotrione compoundswhich are useful as herbicidal agents.

The 1-(3-heterocyclylphenyl)-s-triazine-2,4,6-oxo or thiotrionecompounds of the present invention have the structural formula I##STR2## wherein X and Y are each independently hydrogen, halogen,nitro, cyano, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy or S(O)_(m) R₂ ;

m is an integer of 0, 1 or 2;

R₂ is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl;

R is hydrogen, C₁ -C₆ alkyl, C₂ -C₁₂ alkoxyalkyl, C₃ -C₁₂alkylcarbonylalkyl, C₃ -C₁₂ haloalkylcarbonylalkyl, C₃ -C₁₂alkoxycarbonylalkyl, C₃ -C₁₂ haloalkoxycarbonylalkyl, C₃ -C₆ alkenyl, C₃-C₆ alkynyl, an alkali metal,

phenyl optionally substituted with one to three halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups, or

benzyl optionally substituted with one to three halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups;

R₁ is hydrogen, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, cyano,

C₁ -C₁₂ alkyl optionally substituted with one or more halogen atoms, orone cyano, C(O)R₃, C(W)R₄, OC(O)R₅, CH₂ OC(O)R₅, OR₄, CH₂ OR₄ or CR₆(OR₇)₂ group, or one phenyl group optionally substituted with one tothree halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups,or

phenyl optionally substituted with one to three halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups;

R₃ is OH, OR₈, SR₈ or NR₉ R₁₀ ;

W is O, NOR₉, NCOR₉ or NNHCONH₂ ;

R₄, R₅ and R₆ are each independently hydrogen,

C₁ -C₄ alkyl or C₁ -C₄ haloalkyl;

R₇ is C₁ -C₄ alkyl;

R₈ is C₁ -C₆ alkyl optionally substituted with C₁ -C₄ alkoxy, C₁ -C₄alkylthio, halogen, hydroxy, C₃ -C₆ cycloalkyl, furyl or phenyloptionally substituted with one or more halogen, cyano, nitro, C₁ -C₄alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups,

C₃ -C₆ alkenyl optionally substituted with C₁ -C₄ alkoxy, halogen, C₃-C₆ cycloalkyl or phenyl optionally substituted with one or morehalogen, cyano, nitro, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy orC₁ -C₄ haloalkoxy groups,

C₃ -C₆ alkynyl optionally substituted with C₁ -C₄ alkoxy or halogen,

C₃ -C₆ cycloalkyl,

N═C(R₄ R₅), or

an alkali metal, alkaline earth metal, manganese, copper, zinc, cobalt,silver, nickel, ammonium or organic ammonium cation;

R₉ and R₁₀ are each independently hydrogen,

C₁ -C₆ alkyl,

benzyl optionally substituted with one or more halogen, cyano, nitro, C₁-C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups,or

phenyl optionally substituted with one or more halogen, cyano, nitro, C₁-C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups;

Q is selected from ##STR3## R₁₁ and R₁₂ are each independently hydrogen,C₁ -C₆ alkyl optionally substituted with one or more halogen atoms, or

C₃ -C₆ cycloalkyl optionally substituted with one or more halogen atoms,and

when R₁₁ and R₁₂ are taken together with the atoms to which they areattached, they represent a four- to seven-membered saturated orunsaturated ring optionally interrupted by O, S(O)_(r) or N, andoptionally substituted with one to three methyl groups or one or morehalogen atoms;

R₁₃, R₁₄ and R₁₅ are each independently hydrogen, C₁ -C₃ alkyl or C₁ -C₃haloalkyl;

R₁₆ is hydrogen or halogen;

R₁₇ is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl;

A, A₁, A₂, A₃ and A₄ are each independently O or S;

L is hydroxy, halogen, C₁ -C₃ alkoxy or C₁ -C₃ alkylthio;

M is halogen or C₁ -C₃ alkyl;

Z is N or CH;

Z₁ is NR₉ or O;

Z₂ is OR₇ or NR₉ R₁₀ ;

r is an integer of 0, 1 or 2; and

q is an integer of 2, 3 or 4.

This invention also relates to compositions containing those compoundsand methods for using those compounds and compositions. Advantageously,it has been found that the compounds of the present invention, andcompositions containing them, are useful for the control of undesirableplant species. The compounds of the present invention are especiallyuseful for the selective control of undesirable plant species in thepresence of crops.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a method for controlling undesirableplant species which comprises applying to the foliage of said plants orto the soil or water containing seeds or other propagating organsthereof, a herbicidally effective amount of a formula I,1-(3-heterocyclylphenyl)-s-triazine-2,4,6-oxo or thiotrione compound.

The 1-(3-heterocyclylphenyl)-s-triazine-2,4,6-oxo or thiotrionecompounds of the present invention have the structural formula I##STR4## wherein X, Y, R, R₁, A, A₁, A₂ and Q are as described above.

Preferred formula I compounds of this invention are those wherein

X is hydrogen or halogen;

Y is hydrogen, halogen, nitro or cyano;

R is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxymethyl,

(C₁ -C₄ alkoxy)carbonylmethyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl;

R₁ is hydrogen, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl or C₁ -C₆ alkyloptionally substituted with one C(O)R₃ group;

R₃ is OH or OR₈ ;

R₈ is C₁ -C₆ alkyl or

an alkali metal, ammonium or organic ammonium cation;

Q is selected from ##STR5## R₁₁ and R₁₂ are taken together with theatoms to which they are attached to form a ring in which R₁₁ R₁₂ is a C₂-C₅ alkylene group optionally interrupted by S(O)_(r), and optionallysubstituted with one to three methyl groups or one or more halogenatoms, or R₁₁ R₁₂ is represented by the structure: --CR₁₈ ═CR₁₉ --CR₂₀═CR₂₁ -- where R₁₈, R₁₉, R₂₀ and R₂₁ are each independently hydrogen,halogen or methyl;

A, A₁ and A₂ are O;

A₃ and A₄ are each independently O or S;

Z is N or CH; and

r is an integer of 0, 1 or 2.

More preferred formula I herbicidal agents of the present invention arethose wherein

X and Y are each independently hydrogen, F or Cl;

R is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxymethyl, (C₁ -C₄alkoxy)carbonylmethyl, allyl or propargyl;

R₁ is allyl, propargyl or C₁ -C₄ alkyl optionally subsituted with oneC(O)R₃ group;

R₃ is OH or OR₈ ;

R₈ is C₁ -C₆ alkyl;

Q is selected from ##STR6## R₁₁ and R₁₂ are taken together with theatoms to which they are attached to form a ring in which R₁₁ R₁₂ is abutylene group optionally substituted with one to three methyl groups;

A, A₁ and A₂ are O; and

r is an integer of 0 or 1.

Most preferred formula I compounds of this invention which areespecially useful for the control of undesirable plant species are thosewherein

X is F or Cl;

Y is Cl;

R is C₁ -C₄ alkyl, allyl or propargyl;

R₁ is CH2CO₂ R₈ ;

R₈ is C₁ -C₄ alkyl;

Q is ##STR7## A, A₁ and A₂ are O; and r is an integer of 0 or 1.

1-(3-Heterocyclylphenyl)-s-triazine-2,4,6-oxotrione compounds of thepresent invention which are particularly effective herbicidal agentsinclude:

isopropyl3-{2-chloro-4-fluoro-5-[5,6,8,8a-tetrahydro-1,3-dioxo-1H-imidazo[5,1-c][1,4]thiazin-2(3H)-yl]phenyl}tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate;

isopropyl3-{2-chloro-4-fluoro-5-[(tetrahydro-3-oxo-1H,3H-[1,3,4]thiadiazolo[3,4-a]pyridazin-1-ylidene)amino]phenyl}tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate;

isopropyl3-[2-chloro-4-fluoro-5-(tetrahydro-1,3,7-trioxo-1H-imidazo[5,1-c][1,4]thiazin-2(3H)-yl)phenyl]tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate;

isopropyl3-[2-chloro-4-fluoro-5-(3-fluorophthalimido)phenyl]tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate;

tert-butyl3-[2-chloro-5-(1-cyclohexene-1,2-dicarboximido)-4-fluorophenyl]tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate;

isopropyl3-[2-chloro-5-(1-cyclohexene-1,2-dicarboximido)-4-fluorophenyl]tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate;and

methyl3-[2-chloro-5-(1-cyclohexene-1,2-dicarboximido)-4-fluorophenyl]tetrahydo-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate,among others

Exemplary of halogen hereinabove are flourine, chlorine, bromine andiodine. The terms C₁ -C₄ haloalkyl, C₁ -C₃ haloalkyl, and C₁ -C₄haloalkoxy as used in the specification and claims designates a C₁ -C₄alkyl group, a C₁ -C₃ alkyl group or a C₁ -C₄ alkoxy group substitutedwith one or more halogen atoms, respectively. In formula I above, alkalimetals include: sodium, potassium and lithium. Alkaline earth metals offormula I include magnesium and calcium. Further, the term organicammonium is defined as a group consisting of a positively chargednitrogen atom joined to from one to four aliphatic groups, eachcontaining from one to sixteen carbon atoms.

It has now been found that the compounds of the present invention areespecially useful for the selective control of undesirable plant speciesin the presence of important agronomic crops.

Formula I compounds wherein Q is Q1 may be prepared by reducing a3-(3-nitrophenyl)-s-triazine-2,4,6-oxo or thiotrione of formula II bystandard conditions such as catalytic hydrogenation or chemicalreduction to form an amine of formula III, and reacting the formula IIIamine with an anhydride of formula IV, preferably at an elevatedtemperature in the presence of an acid such as acetic acid to form theformula I compound wherein R₁ is hydrogen, and optionally alkylating theformula I compound wherein R₁ is hydrogen with an alkylating agent offormula V and a base to form the formula I compound wherein R₁ is otherthan hydrogen. The reactions are shown in Flow Diagram I. ##STR8##

Alternatively, formula I compounds wherein Q is Q1 and R₁ is other thanhydrogen and may be prepared by alkylating a3-(3-nitrophenyl)-s-triazine-2,4,6-oxo or thiotrione of formula II withan alkylating agent of formula V and a base to form a3-(3-nitrophenyl)-s-triazine-2,4,6-oxo or thiotrione of formula VI,reducing the formula VI compound by standard conditions to form an amineof formula VII, and reacting the formula VII amine with an anhydride offormula IV, preferably at an elevated temperature, in the presence of anacid such as acetic acid. The reaction scheme is shown in Flow DiagramII. ##STR9##

Formula I compounds wherein Q is Q2 and Z is CH may be prepared byreacting an amine of formula VII with phosgene or thiophosgene in thepresence of an inert solvent to form an isocyanate or thioisocyanate offormula VIII, reacting the formula VIII isocyanate or thioisocyanatewith an aminoester of formula IX in the presence of a base such astriethylamine to form an intermediate compound, and cyclizing theintermediate compound with an acid or base in the presence of an inertorganic solvent such as ethanol. The reactions are shown in Flow DiagramIII. ##STR10##

Compounds of formula I wherein Q is Q2 and Z is nitrogen may be preparedby reacting an isocyanate or thioisocyanate of formula VIII with asubstituted hydrazine of formula X to form an intermediate compound, andcyclizing the intermediate compound with base. The reaction scheme isshown below in Flow Diagram IV. ##STR11##

Formula I compounds wherein Q is Q3 may be prepared by reacting an amineof formula III with sodium nitrite, sodium azide, acetic acid,hydrochloric acid and sodium acetate or with sodium nitrite, hydrazinehydrate and acetic acid to form an azide of formula XI, and reacting theformula XI azide with an isocyanate of formula XII to form the desiredformula I compound wherein R₁ is hydrogen, and optionally alkylating theformula I compound wherein R₁ is hydrogen with an alkylating agent offormula V and a base. The reactions are shown in Flow Diagram V.##STR12##

Compounds of formula I wherein Q is Q4 may be prepared by reacting acompound of formula I wherein Q is Q1 and A₃ and A₄ are oxygen withsodium borohydride to form a compound wherein L is OH, reacting thecompound wherein L is OH with a base and a suitable alkylating agent toform a compound wherein L is C₁ -C₃ alkoxy or reacting the compoundwherein L is OH with a halogenating agent such as phosphorustrichloride, thionyl chloride, phosphorus tribromide, triphenylphosphine-bromine, phosphorus triiodide or triphenyl phosphine-iodine inan inert solvent such as chloroform to form a compound wherein L ishalogen and further reacting the compound wherein L is halogen with a C₁-C₃ alkyl sulfide to form a compound wherein L is C₁ -C₃ alkylthio. Theabove reaction schemes are shown below in Flow Diagram VI. ##STR13##

Formula I compounds wherein Q is Q5 may be prepared by diazotizing anamine of formula VII by standard methods to form an intermediatecompound which is reduced with sodium sulfite to form a hydrazine offormula XIV. The hydrazine is then reacted with an imino ether offormula XV to form an amidrazone of formula XVI, and reacting theamidrazone with phosgene or a suitable phosgene equivalent optionally inthe presence of triethylamine to form the desired compound. Thereactions are shown in Flow Diagram VII. ##STR14##

Compounds of formula I wherein Q is Q6 may be prepared by condensing anamine of formula VII with a β-aminoaldehyde of formula XVII in thepresence of a base to form an intermediate compound, and reacting theintermediate compound with phosgene or a phosgene equivalent, Thereactions are shown in Flow Diagram VIII. ##STR15##

Formula I compounds wherein Q is Q7 may be prepared by reacting anisocyanate of formula VIII with a substituted alkyne of formula XVIII inthe presence of a base, optionally at an elevated temperature. Thereaction is shown in Flow Diagram IX. ##STR16##

Formula I compounds wherein Q is Q8 and M is halogen may be prepared byreacting a hydrazine of formula XIV or its hydrochloride salt with a2-alkoxycarbonylalkanone of formula XIX optionally in the presence of abase such as triethylamine or sodium acetate in an inert solvent such asethanol or toluene to form a 2,3-dihydropyrazol-3-one of formula XX, andhalogenating the formula XX compound with a halogenating agent such asphosphorus oxychloride or phosphorus oxybromide. The reactions are shownin Flow Diagram X. ##STR17##

Formula I compounds wherein Q is Q8 and M is C₁ -C₃ alkyl may beprepared by reacting a hydrazine of formula XIV with a 1,3-diketone offormula XXI optionally in the presence of a base in an inert solvent.The reaction is shown below in Flow Diagram XI. ##STR18##

Compounds of formula I wherein Q is Q9 may be prepared by diazotizing anamine of formula VII to form an intermediate diazonium salt and reactingthe intermediate salt in situ with a β-aminoacid of formula XXII in thepresence of triethylamine. The reaction scheme is shown below in FlowDiagram XII. ##STR19##

Compounds of formula I wherein Q is Q10 may be prepared by reacting ahydrazine of formula XIV with an acyl halide of formula XXIII in thepresence of a base such as triethylamine or pyridine to form an arylhydrazide of formula XXIV, and reacting the aryl hydrazide withtrichloromethyl chloroformate, phosgene or a suitable phosgeneequivalent optionally in the presence of triethylamine. The reactionscheme is shown in Flow Diagram XIII. ##STR20##

Formula I compounds wherein Q is Q11, A₃ is sulfur, A₄ is oxygen and Zis CH may be prepared by reacting an isothiocyanate of formula VIII withan amine of formula XXV to form a thiourea of formula XXVI and reactingthe thiourea with an α-halocarbonyl halide of formula XXVII in thepresence of a base. The reactions are shown in Flow Diagram XIV.##STR21##

Formula I compounds wherein Q is Q11, A₃ is sulfur, A₄ is oxygen and Zis nitrogen may be prepared by reacting an isothiocyanate of formulaVIII with a substituted hydrazine of formula XXVIII to form anintermediate compound of formula XXIX and reacting the intermediatecompound with phosgene or a suitable phosgene equivalent in the presenceof a base such as triethylamine. The reaction sequence is shown in FlowDiagram XV. ##STR22##

Compounds of formula I wherein Q is Q11, A₃ and A₄ are oxygen and Z isCH may be prepared by reacting an isocyanate of formula VIII with anamine of formula XXV to form a urea of formula XXX, dehydrating the ureato form a carbodiimide of formula XXXI, reacting the carbodiimide withan α-halocarbonyl halide of formula XXVII to form a haloamidine offormula XXXII, hydrolyzing the haloamidine with aqueous acid to form anacylurea, heating the acylurea in situ to form an O-acylurea of formulaXXXIII, and reacting the O-acylurea with a base such as triethylamine.The reactions are shown below in Flow Diagram XVI. ##STR23##

Formula I compounds wherein Q is Q12 may be prepared by reacting anamine of formula VII with an anhydride of formula IV to form anacid-amide of formula XXXIV, and dehydrating the acid-amide with adehydrating agent such as 1,3-dicyclohexylcarbodiimide. The reactionscheme is shown below in Flow Diagram XVII. ##STR24##

Compounds of formula I wherein Q is Q13 may be prepared by reacting athiourea of formula XXVI with iodomethane to form an isothiourea offormula XXXV and reacting the isothiourea with a chlorooxime of formulaXXXVI. The reaction scheme is shown in Flow Diagram XVIII. ##STR25##

Formula I compounds wherein Q is Q14 may be prepared by reacting anamine of formula VII with a chloroformate of formula XXXVII to form acarbamate of formula XXXVIII, and reacting the carbamate with ahaloketone of formula XXXIX in the presence of a base. The reactionscheme is shown below in Flow Diagram XIX. ##STR26##

Compounds of formula I wherein Q is Q15 may be prepared by reacting anamine of formula VII with ethyl chloroformate to form a carbamate offormula XL, and reacting the carbamate with a hydroxy ester of formulaXLI at an elevated temperature with removal of ethanol. The reactionsare shown in Flow Diagram XX. ##STR27##

Alternatively, compounds of formula I wherein Q is Q15 may be preparedby reacting an isocyanate of formula VIII with a hydroxy ester offormula XLII to form an intermediate compound of formula XLIII, andreacting the intermediate compound with a base such as sodium acetate inan inert solvent such as toluene. The reaction scheme is shown below inFlow Diagram XXI. ##STR28##

Formula I compounds wherein Q is Q16 may be prepared by reacting anisocyanate of formula VIII with an α-amino-α,β-unsaturated ester offormula XLIV to form a urea of formula XLV, and reacting the urea with abase such as sodium acetate in an inert solvent such as toluene at anelevated temperature. The reactions are shown in Flow Diagram XXII.##STR29##

Alternatively, formula I compounds wherein Q is Q16 may be prepared byreacting an isocyanate of formula VIII with an amino acid of formulaXLVI to form a urea of formula XLVII, reacting the urea with aqueousacid to form a hydantoin of formula XLVIII, and reacting the hydantoinwith an acetal of formula XLIX. The reaction scheme is shown below inFlow Diagram XXIII. ##STR30##

Compounds of formula I wherein Q is Q17 may be prepared by reacting anisocyanate of formula VIII with a hydroxy alkenoate of formula L in thepresence of a base such as triethylamine. The reaction is shown in FlowDiagram XXIV. ##STR31##

Compounds of formula I wherein Q is Q18 may be prepared by reacting anamine of formula VII with an anhydride of formula LI in the presence ofan acid such as acetic acid preferably at an elevated temperature. Thereaction is shown below in Flow Diagram XXV. ##STR32##

Formula I compounds wherein Q is Q19 may be prepared by reacting aformula I compound wherein Q is Q1, A₃ and A₄ are oxygen and R₁ ishydrogen with a Grignard Reagent of formula LII in a solvent such asdiethyl ether or tetrahydrofuran at an elevated temperature to form anintermediate compound of formula LIII, and reacting the intermediatecompound with potassium bisulfate at an elevated temperature to form thedesired formula I compound wherein R₁ is hydrogen, and optionallyalkylating the formula I compound wherein R₁ is hydrogen with analkylating agent of formula V in the presence of a base. The reactionsare shown in Flow Diagram XXVI. ##STR33##

Formula I compounds wherein Q is Q20 may be prepared by reacting anamine of formula VII with an anhydride of formula LIV in aceticanhydride with a catalytic amount of sodium acetate at an elevatedtemperature, in acetic acid at an elevated temperature or in xylene witha catalytic amount of p-toluene sulfonic acid at an elevatedtemperature. The reaction is shown below in Flow Diagram XXVII.##STR34##

Alternatively, formula I compounds wherein Q is Q20 may be prepared byreacting an amine of formula VII with a diacid of formula LV in xyleneat reflux. The reaction is shown in Flow Diagram XXVIII. ##STR35##

Compounds of formula I wherein Q is Q21 may be prepared by reacting anamine of formula VII with ethyl malonyldiurethane and sodium nitrite inacetic acid with a catalytic amount of concentrated hydrochloric acid toform a hydrazone of formula LVI, cyclizing the hydrazone with base toform a triazinedione of formula LVII, and decarboxylating thetriazinedione with mercaptoacetic acid at an elevated temperature andoptionally alkylating the formula I compound wherein Q is Q21 and R₁₁ ishydrogen with an alkyl halide and a base such as sodium hydride. Thereactions are shown in Flow Diagram XXIX. ##STR36##

Alternatively, compounds of formula I wherein Q is Q21 and R₁₁ ishydrogen may be prepared by reacting a hydrazine of formula XIV withacetone in a sulfuric acid solution to form a hydrazone of formulaLVIII, reacting the hydrazone with potassium cyanate in an acetic acidsolution to form a triazolidine of formula LIX, and reacting thetriazolidine with glyoxylic acid and sulfuric acid. The reactionsequence is shown below in Flow Diagram XXX. ##STR37##

Formula I compounds wherein Q is Q22 and R₁ is other than hydrogen maybe prepared by reacting an isocyanate of formula VIII with an aminoester of formula LX in the presence of a base such as sodium hydride toform an intermediate compound of formula LXI, and cyclizing theintermediate compound optionally in the presence of acid or base, andoptionally alkylating the formula I compound wherein Q is Q22 and R₁₆ ishydrogen with a C₁ -C₃ alkyl halide and a base such as sodium hydride.The reaction scheme is shown in Flow Diagram XXXI. ##STR38##

Formula I compounds wherein Q is Q23 may be prepared by reacting anamine of formula LXII with an α,β-unsaturated ester of formula LXIII toform an amino ester of formula LXIV, and reacting the amino ester withan isocyanate of formula VIII followed by heating under acidicconditions. The reaction sequence is shown below in Flow Diagram XXXII.##STR39##

Compounds of formula I wherein Q is Q24 may be prepared by reacting ahydrazine of formula XIV with a formylpropionate of formula LXV followedby cyclization under acidic conditions to form a dihydropyridazinone offormula LXVI, and dehydrogenating the dihydropyridazinone with chloranilor 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) in an inert solvent suchas dioxane or toluene at an elevated temperature. The reactions areshown in Flow Diagram XXXIII. ##STR40##

Compounds of formula I wherein Q is Q25 may be prepared by reacting anisocyanate of formula VIII with an acetonide of formula LXVII at anelevated temperature. The reaction is shown in Flow Diagram XXXIV.##STR41##

Formula I compounds wherein Q is Q26 may be prepared by reacting a3-(substituted phenyl)-s-triazine-2,4,6-oxo or thiotrione of formulaLXVIII with acetyl chloride in the presence of aluminum chloride to forma ketone of formula LXIX, reacting the ketone with an ester of formulaLXX to form a diketone compound of formula LXXI, and reacting thediketone compound with a hydrazine of formula LXXII to form the formulaI compound wherein Q is Q26 and R₁₆ is hydrogen, and optionallyhalogenating the formula I compound wherein Q is Q26 and R₁₆ ishydrogen. The reactions are shown below in Flow Diagram XXXV. ##STR42##

Compounds of formula I wherein Q is Q27 may be prepared by reacting aketone of formula LXIX with a carbonate or thiocarbonate of formulaLXXIII in the presence of a base to form an ester or thioxoester offormula LXXIV, reacting the ester or thioxoester with a hydrazine offormula LXXII to form an intermediate compound of formula LXXV, andalkylating the intermediate compound with an alkylating agent of formulaLXXVI in the presence of a base to form the formula I compound wherein Qis Q27 and R₁₆ is hydrogen, and optionally halogenating the formula Icompound wherein Q is Q27 and R₁₆ is hydrogen. The reaction scheme isshown in Flow Diagram XXXVI. ##STR43##

Formula I compounds wherein Q is Q28 may be prepared by reacting ananiline of formula LXXVII with an isocyanate or isothiocyanate offormula LXXVIII to form a urea or thiourea of formula LXXIX, cyclizingthe urea or thiourea with an isocyanate or thioisocyanate of formulaLXXX to form a 3-(substituted phenyl)-s-triazine-2,4,6-oxo or thiotrioneof formula LXXXI, reacting the 3-(substitutedphenyl)-s-triazine-2,4,6-oxo or thiotrione sequentially with base,thionyl chloride and a hydrazine of formula LXXII to form anintermediate compound of formula LXXXII, and reacting the intermediatecompound with phosgene or a phosgene equivalent to form the formula Icompound wherein Q is Q28 and R₁ is hydrogen, and optionally alkylatingthe formula I compound wherein Q is Q28 and R₁ is hydrogen with analkylating agent of formula V in the presence of a base. The reactionsare shown in Flow Diagram XXXVII. ##STR44##

Compounds of formula I wherein Q is Q29 may be prepared by reacting aketone of formula LXIX with an amidine of formula LXXXIII to form aformula I compound wherein Q is Q29 and R₁₆ is hydrogen, and optionallyhalogenating the formula I compound wherein Q is Q29 and R₁₆ ishydrogen. The reaction scheme is shown in Flow Diagram XXXVIII.##STR45##

Formula I compounds wherein Q is Q30 and R₁ is hydrogen may be preparedby reacting an amine of formula LXXXIV with an isocyanate orthioisocyanate of formula LXXVIII to form a urea or thiourea of formulaLXXXV, cyclizing the urea or thiourea with an isocyanate orisothiocyanate of formula LXXX to form a 3-(substitutedphenyl)-s-triazine-2,4,6-oxo or thiotrione of formula LXXXVI, reactingthe 3-(substituted phenyl)-s-triazine-2,4,6-oxo or thiotrionesequentially with ammonium hydroxide and a chlorinating agent to form achlorooxime of formula LXXXVII, and reacting the chlorooxime with analkyne of formula LXXXVIII to obtain a formula I compound wherein Q isQ30, R₁ is hydrogen and Z₂ is C₁ -C₄ alkoxy, and optionally reactingthat compound sequentially with acid or base, thionyl chloride and anamine of formula LXXXIX to obtain a formula I compound wherein Q is Q30,R₁ is hydrogen and Z₂ is NR₉ R₁₀. The reactions are shown in FlowDiagram XXXIX. ##STR46##

Compounds of formula I wherein Q is Q30 and R₁ is other than hydrogenmay be prepared by alkylating a formula I compound wherein Q is Q30 andR₁ is hydrogen with an alkylating agent of formula V in the presence ofa base. The reaction is shown in Flow Diagram XL. ##STR47##

Formula I compounds wherein Q is Q31 may be prepared by reacting a3-(substituted phenyl)-s-triazine-2,4,6-oxo or thiotrione of formulaLXVIII with an ester of formula XC in the presence of aluminum chlorideto form an intermediate compound of formula XCI, and reacting theintermediate compound with a substituted amine of formula XCII. Thereaction scheme is shown in Flow Diagram XLI. ##STR48##

Compounds of formula I wherein Q is Q32 may be prepared by reacting anisocyanate or thioisocyanate of formula VIII with an aminoester oraminothionoester of formula XCIII in an inert solvent preferably at anelevated temperature. The reaction is shown in Flow Diagram XLII.##STR49##

Compounds of formula I wherein R₃ is NR₉ R₁₀ may be prepared usingstandard procedures such as hydrolyzing the appropriate ester of formulaXCIV in the presence of trifluoroacetic acid, reacting the resultantacid with thionyl chloride to give the acid chloride of formula XCV, andreacting the formula XCV acid chloride with an amine of formula LXXXIXoptionally in the presence of base to give the desired product. Thereactions are shown in Flow Diagram XLIII. ##STR50##

Using the formula XCV acid chloride, formula I compounds wherein R₁ isC₁ -C₁₂ alkyl substituted with one C(O)C₁ -C₄ alkyl group may beprepared as shown below in Flow Diagram XLIV. ##STR51##

Formula I compounds wherein R₃ is SR₈ may be prepared by reacting theformula XCV acid chloride with a thiol of formula XCVI. The reaction isshown below in Flow Diagram XLV. ##STR52##

Formula I compounds wherein R₁ is C₁ -C₁₂ alkyl substituted with oneCH2OR₄ group may be prepared by reducing a compound of formula XCVII toform the formula I compound wherein R₄ is hydrogen, and optionallyreacting the formula I compound wherein R₄ is hydrogen with a C₁ -C₄alkyl halide in the presence of a base. The reactions are shown below inFlow Diagram XLVI. ##STR53##

Similarly, compounds of formula I wherein R₁ is C₁ -C₁₂ alkylsubstituted with one CH₂ OC(O)R₅ group may be prepared by reacting theformula I compound wherein R₁ is C₁ -C₁₂ alkyl substituted with one CH₂OH group with an acid halide of formula XCVIII in the presence of abase. The reaction is shown in Flow Diagram XLVII. ##STR54##

Formula I compounds wherein R₁ is C₁ -C₁₂ alkyl substituted with one CHOor CH(OR₆)₂ group may be prepared by reducing the formula XCVII compoundto form an aldehyde of formula XCIX, and reacting the aldehyde with analcohol of formula C in the presence of an acid. The reactions are shownin Flow Diagram XLVIII. ##STR55##

Compounds of formula I wherein R₁ is C₁ -C₁₂ alkyl substituted with oneHC═NOR₉ group may be prepared by reacting the formula XC[X aidehyde withan amine of formula CI. The reaction is shown in Flow Diagram XLIX.##STR56##

Similarly, compounds of formula I wherein R₁ is C₁ -C₁₂ alkylsubstituted with HC═NCOR₉ or HC═NNHCONH₂ may be prepared by reacting theformula XCIX aldehyde with an amine of formula CII or a hydrazine offormula CIII. The reactions are shown in Flow Diagram L. ##STR57##

Formula I compounds wherein R₁ is C₁ -C₁₂ alkyl substituted with cyanomay be prepared by dehydrating an amide of formula CIV using standardconditions. The reaction is shown in Flow Diagram LI. ##STR58##

Formula I compounds wherein R₈ is an alkali metal, alkaline earth metal,manganese, copper, zinc, cobalt, silver, nickel, ammonium or organicammonium cation, and/or R is an alkali metal, may be prepared fromformula I compounds wherein R₃ is OH and/or R is hydrogen byconventional processes known to those skilled in the art.

Compounds of formula I may also be prepared by nitrating aheterocyclylphenyl compound of formula CV with nitric acid to form a3-nitro-1-heterocyclylphenyl compound of formula CVI, reducing the3-nitro-1-heterocyclylphenyl compound using standard conditions to forma 3-amino-1-heterocyclylphenyl compound of formula CVII, reacting the3-amino-1-heterocyclylphenyl compound with an isocyanate orisothiocyanate of formula LXXVIII to form a urea or thiourea of formulaCVIII, and cyclizing the urea or thiourea with an isocyanate orisothiocyanate of formula LXXX to obtain a formula I compound wherein R₁is hydrogen, and optionally alkylating the formula I compound wherein R₁is hydrogen with an alkylating agent of formula V in the presence of abase. The reactions are shown in Flow Diagram LII. ##STR59##

Starting formula II compounds wherein A, A₁ and A₂ are oxygen may beprepared by reacting an amide of formula CIX with sodium hypochloriteand sodium hydroxide to form an isocyanate of formula CX, reacting theisocyanate with an amine of formula CXI to form a urea of formula CXII,cyclizing the urea with N-(chlorocarbonyl) isocyanate to form a trioneof formula CXIII, and nitrating the trione with nitric acid. Thereaction sequence is shown in Flow Diagram LIII. ##STR60##

Formula II compounds wherein A and A₂ are oxygen and A₁ is sulfur may beprepared by nitrating a urea of formula CXII to form an intermediatecompound of formula CXIV, reacting the formula CXIV compound with anisothiocyanate of formula CXV to form an intermediate compound offormula CXVI, and cyclizing the formula CXVI compound with base. Thereaction scheme is shown in Flow Diagram LIV. ##STR61##

Compounds of formula II wherein A is oxygen or sulfur, A₁ is sulfur andA₂ is oxygen may be prepared by reacting an isocyanate of formula CXwith aqueous base to form an amine of formula CXVII, reacting the aminewith an isocyanate or isothiocyanate of formula LXXVIII to form a ureaof formula CXVIII, nitrating the urea to obtain an intermediate compoundof formula CXIX, reacting the formula CXIX compound with anisothiocyanate of formula CXV to form an intermediate compound offormula CXX, and cyclizing the formula CXX compound with base. Thereactions are shown in Flow Diagram LV. ##STR62##

Formula II compounds wherein A is sulfur and A₁ and A₂ are oxygen may beprepared by nitrating an amine of formula CXVII to obtain a3-nitroaniline of formula CXXI, reacting to the 3-nitroaniline with anisothiocyanate of formula CXXII to form a thiourea of formula CXXIII,and cyclizing the thiourea with N-(chlorocarbonyl) isocyanate. Thereaction scheme is shown in Flow Diagram LVI. ##STR63##

Compounds of formula VI Wherein A and A₁ are sulfur and A₂ is oxygen orsulfur may be prepared by reacting a thiourea of formula CXXIII with anisothiocyanate of formula CXXIV to form an intermediate compound offormula CXXV, and cyclizing the intermediate compound with phosgene orthiophosgene. The reactions are shown below in Flow Diagram LVII.##STR64##

Compounds of formula VI wherein A and A₁ are each independently oxygenor sulfur and A₂ is sulfur may be prepared by reacting an amine offormula CXXI with an isothiocyanate of formula CXXIV to form a thioureaof formula CXXVI, reacting the thiourea with an isocyanate orisothiocyanate of formula CXXVII to form an intermediate compound offormula CXXVIII, and cyclizing the intermediate compound with phosgeneor thiophosgene. The reactions are shown in Flow Diagram LVIII.##STR65##

Starting formula CV compounds wherein Q is Q1 may be prepared byreacting an aniline of formula CXXIX with an anhydride of formula IV inthe presence of an acid such as acetic acid. The reaction is shown inFlow Diagram LIX. ##STR66##

Compounds of formula CV wherein Q is Q2 and Z is CH may be prepared byreacting an isocyanate of formula CXXX with an aminoester of formula IXin the presence of a base, and optionally thionating the resultantcompound with a thionating agent such as Lawesson's reagent or P₄ S₁₀.The reactions are shown in Flow diagram LX. ##STR67##

Starting formula CV compounds wherein Q is Q2 and Z is nitrogen may beprepared by reacting an isocyanate of formula CXXX with a substitutedhydrazine of formula XXVIII to form an intermediate compound of formulaCXXXI, and reacting the intermediate compound with phosgene orthiophosgene to form a formula CV compound wherein Q is Q2, z isnitrogen and A₃ is oxygen, and optionally thionating the formula CVcompound wherein Q is Q2, Z is nitrogen and A₃ is oxygen. The reactionscheme is shown in Flow Diagram LXI. ##STR68##

Compounds of formula CV wherein Q is Q11, A₃ is sulfur, A₄ is oxygen andZ is CH may be prepared by reacting an isothiocyanate of formula CXXXIIwith an amine of formula XXV to form a thiourea of formula CXXXIII, andreacting the thiourea with an α-halocarbonyl halide of formula XXVII inthe presence of a base. The reactions are shown in Flow Diagram LXII.##STR69##

Starting compounds of formula CV wherein Q is Q11, A₃ is sulfur, A₄ isoxygen and Z is nitrogen may be prepared by reacting an isothiocyanateof formula CXXXII with a substituted hydrazine of formula XXVIII to forman intermediate compound of formula CXXXIV, and reacting theintermediate compound with phosgene or a suitable phosgene equivalent inthe presence of a base such as triethylamine. The reaction sequence isshown in Flow Diagram LXIII. ##STR70##

Compounds of formula CV wherein Q is Q11, A₃ and A₄ are oxygen and Z isCH may be prepared by reacting an isocyanate of formula CXXX with anamine of formula XXV to form a urea of formula CXXXV, dehydrating theurea to form a carbodiimide of formula CXXXVI, reacting the carbodiimidewith an α-halocarbonyl halide of formula XXVII to form a haloamidine offormula CXXXVII, hydrolyzing the haloamidine with aqueous acid to forman acylurea, heating the acylurea in situ to form an O-acylurea offormula CXXXVIII, and reacting the O-acylurea with a base such astriethylamine. The reactions are shown in Flow Diagram LXIV. ##STR71##

This invention also relates to intermediate compounds which are usefulin the preparation of the formula I compounds. The intermediatecompounds have the structural formula CXXXIX ##STR72## wherein T is NH₂,--NCO, --NCS, --N₃, --NHNH₂, --NHC(S)NHR₁₁, --C(O)NHNHR₁₃, --C(O)H,--C(O)CH₃, --C(O)CO₂ (C₁ -C₄ alkyl), --C(O)CH₂ C(O)R₁₁, --C(O)CH₂C(A₃)O(C₁ -C₄ alkyl), --CO₂ (C₁ -C₄ -alkyl), --N═C═NR₁₁, --NHC(O)NHR₁₁,--NHC(S)NR₁₁ HNR₁₂, --N═C(SCH₃)NHR₁₁, --NHCO₂ (C₁ -C₄ alkyl),--C(C₁)═NOH, ##STR73## X and Y are each independently hydrogen, halogen,nitro, cyano, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy or S(O)_(m) R₂ ;

m is an integer of 0, 1 or 2;

R₂ is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl;

R is hydrogen, C₁ -C₆ alkyl, C₂ -C₁₂ alkoxyalkyl, C₃ -C₁₂alkylcarbonylalkyl, C₃ -C₁₂ haloalkylcarbonylalkyl, C₃ -C₁₂alkoxycarbonylalkyl, C₃ -C₁₂ haloalkoxycarbonylalkyl, C₃ -C₆ alkenyl, C₃-C₆ alkynyl,

phenyl optionally substituted with one to three halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups, or

benzyl optionally substituted with one to three halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups;

R₁ is hydrogen, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, cyano,

C₁ -C₁₂ alkyl optionally substituted with one or more halogen atoms, orone cyano, C(O)R₃, OC(O)R₅, CH₂ OC(O)R₅, OR₄, CH₂ OR₄ or CR₆ (OR₇)₂group, or one phenyl group optionally substituted with one to threehalogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups, or

phenyl optionally substituted with one to three halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups;

R₃ is OR₈, SR₈ or NR₉ R₁₀ ;

R₄, R₅ and R₆ are each independently hydrogen, C₁ -C₄ alkyl or C₁ -C₄haloalkyl;

R₇ is C₁ -C₄ alkyl;

R₈ is C₁ -C₆ alkyl optionally substituted with C₁ -C₄ alkoxy, C₁ -C₄alkylthio, halogen, hydroxy, C₃ -C₆ cycloalkyl, furyl or phenyloptionally substituted with one or more halogen, cyano, nitro, C₁ -C₄alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups,

C₃ -C₆ alkenyl optionally substituted with C₁ -C₄ alkoxy, halogen, C₃-C₆ cycloalkyl or phenyl optionally substituted with one or morehalogen, cyano, nitro, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy orC₁ -C₄ haloalkoxy groups,

C₃ -C₆ alkynyl optionally substituted with C₁ -C₄ alkoxy or halogen, or

C₃ -C₆ cycloalkyl;

R₉ and R₁₀ are each independently hydrogen, C₁ -C₆ alkyl,

benzyl optionally substituted with one or more halogen, cyano, nitro, C₁-C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups,or

phenyl optionally substituted with one or more halogen, cyano, nitro, C₁-C₄ alkyl, C₁ -C₄ haloalkyl C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups;

R₁₁ and R₁₂ are each independently hydrogen,

C₁ -C₆ alkyl optionally substituted with one or more halogen atoms, or

C₃ -C₆ cycloalkyl optionally substituted with one or more halogen atoms,and

when R₁₁ and R₁₂ are taken together with the atoms to which they areattached, they represent a four- to seven-membered saturated orunsaturated ring optionally interrupted by O, S(O)_(r) or N, andoptionally substituted with one to three methyl groups or one or morehalogen atoms;

R₁₃ is hydrogen, C₁ -C₃ alkyl or C₁ -C₃ haloalkyl;

A, A₁, A₂, and A₃ are each independently O or S; and

r is an integer of 0, 1 or 2.

Preferred formula CXXXIX intermediate compounds are those wherein

T is NH₂, --NCO, --NCS, --N₃, --NHNH₂, --NHC(S)NHR₁₁, --NHC(O)NHR₁₁,--NHC(S)NR₁₁ NHR₁₂ or --N═C═NR₁₁ ;

X is hydrogen or halogen;

Y is hydrogen, halogen, nitro or cyano;

R is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxymethyl, (C₁ -C₄alkoxy)carbonylmethyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl;

R₁ is hydrogen, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl or C₁ -C₆ alkyloptionally substituted with one CO₂ R₈ group;

R₈ is C₁ -C₆ alkyl;

R₁₁ and R₁₂ are each independently hydrogen or C₁ -C₄ alkyl, and whenR₁₁ and R₁₂ are taken together with the atoms to which they areattached, they form a ring in which R₁₁ R₁₂ is a C₂ -C₅ -alkylene groupoptionally interrupted by S(O)_(r), and optionally substituted with oneto three methyl groups or one or more halogen atoms;

A, A₁ and A₂ are O; and

r is an integer of 0, 1 or 2.

More preferred formula CXXXIX intermediate compounds of this inventionare those wherein

T is NH₂, --NCO, --NCS, --NHC(S)NHR₁₁ or --NHC(O)NHR₁₁ ;

X and Y are each independently hydrogen, F or Cl;

R is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxymethyl, (C₁ -C₄ alkoxy)carbonylmethyl, allyl or propargyl;

R₁ is hydrogen, allyl, propargyl or C₁ -C₄ alkyl optionally substitutedwith one CO₂ R₈ group;

R₈ is C₁ -C₄ alkyl;

R₁₁ is hydrogen or C₁ -C₄ alkyl; and

A, A₁ and A₂ are O.

This invention also relates to intermediate compounds having thestructural formula CXL. ##STR74## wherein T₁ is NO₂, NH₂ or --NHC(A)NHR;

A, A₃ and A₄ are each independently O or S;

X and Y are each independently hydrogen, halogen, nitro,

cyano, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy,

C₁ -C₄ haloalkoxy or S(O)_(m) R₂ ;

m is an integer of 0, 1 or 2;

R₂ is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl;

R is hydrogen, C₁ -C₆ alkyl, C₂ -C₁₂ alkoxyalkyl, C₃ -C₁₂alkylcarbonylalkyl, C₃ -C₁₂ haloalkylcarbonylalkyl,

C₃ -C₁₂ alkoxycarbonylalkyl, C₃ -C₁₂ haloalkoxycarbonylalkyl, C₃ -C₆alkenyl, C₃ -C₆ alkynyl,

phenyl optionally substituted with one to three halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups, or

benzyl optionally substituted with one to three halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups;

R₁₁ and R₁₂ are each independently hydrogen,

C₁ -C₆ alkyl optionally substituted with one or more halogen atoms, or

C₃ -C₆ cycloalkyl optionally substituted with one or more halogen atoms,and

when R₁₁ and R₁₂ are taken together with the atoms to which they areattached, they represent a four- to seven-membered saturated orunsaturated ring optionally interrupted by O, S(O)_(r) or N, andoptionally substituted with one to three methyl groups or one or morehalogen atoms; and

r is an integer of 0, 1 or 2.

Preferred formula CXL intermediate compounds are those wherein

T₁ is NO₂, NH₂ or --NHC(O)NHR;

A₃ and A₄ are O;

X and Y are each independently hydrogen or halogen;

R is C₁ -C₆ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl;

R₁₁ and R₁₂ are taken together with the atoms to which they are attachedto form a ring in which R₁₁ R₁₂ is a C₂ -Csalkylene group optionallyinterrupted by S(O)_(r), and optionally substituted with one to threemethyl groups or one or more halogen atoms, or R₁₁ R₁₂ is represented bythe structure: --CR₁₈ ═CR₁₉ --CR₂₀ ═CR₂₁ -- where R₁₈, R₁₉, R₂₀ and R₂₁are each independently hydrogen, halogen or methyl; and

r is an integer of 0, 1 or 2.

More preferred intermediate compounds of formula CXL are those wherein

T₁ is NO₂, NH₂ or --NHC(O)NHR;

A₃ and A₄ are O;

X is F or Cl;

Y is Cl;

R is C₁ -C₄ alkyl, allyl or propargyl; and

R₁₁ and R₁₂ are taken together with the atoms to which they are attachedto form a ring in which R₁₁ R₁₂ is a butylene group optionallysubstituted with one to three methyl groups.

The formula I compounds of the present invention are effectiveherbicidal agents useful for the control of a wide variety ofundesirable plant species. Those compounds are effective for controllingweeds native to both dry land and wet land areas. The compounds are alsouseful as aquatic herbicides and are effective in controlling theabove-said plants when applied to the foliage thereof or to soil orwater containing seeds or other propagating organs thereof such asstolons, tubers or rhizomes, at rates of from about 0.016 to 4.0 kg/haand preferably from about 0.032 to 2.0 kg/ha.

The formula I compounds of this invention are best suited for use asbroad spectrum herbicides, especially when applied postemergence to thelocus in which weed control is desired. However, certain compounds ofthis invention are selective. In fact, some of the compounds of thisinvention are selective in crops such as soybeans, rice and corn.

While the formula I compounds of this invention are effective forcontrolling undesirable plant species when employed alone, they may alsobe used in combination with other biological chemicals, including otherherbicides.

The formula I compounds of this invention may be applied to crops in theform of a solid or liquid herbicidal composition, comprising aherbicidally effective amount of the compound dispersed or dissolved inan agronomically acceptable, inert solid or liquid carrier. Thecompositions may be applied as preemergence or postemergence treatments.

The formula I compounds may be formulated as emulsifiable concentrates,wettable powders, granular formulations, flowable concentrates and thelike.

In order to facilitate a further understanding of the invention, thefollowing examples are presented primarily for the purpose ofillustrating more specific details thereof. The invention should not bedeemed limited by the examples as the full scope of the invention isdefined in the claims. The term NMR designates nuclear magneticresonance spectroscopy.

EXAMPLE 1 Preparation of 1-(2-Chloro-4-fluorophenyl)-3-methylurea##STR75##

A mixture of 50% sodium hydroxide solution (28 g, 0.35 mol) and 5%sodium hypochlorite solution (226 mL) is added to a mixture of2'-chloro-4'-fluorobenzamide (50 g, 0.288 mol) in methanol at 0° C.After the addition is complete, 55 mL of a 40% methylamine solution isadded at 0° C. The resultant reaction mixture is heated to and stirredat 55° C. for 6 hours, cooled to room temperature and filtered to obtaina solid. The solid is washed sequentially with water and hexanes andair-dried to give the title product as a white solid (30 g, mp 174°-178°C.).

Using essentially the same procedure, but substituting2',4'-dichlorobenzamide for 2'-chloro-4'-fluorobenzamide,1-(2,4-dichlorophenyl)-3-methylurea is obtained as a beige solid.

EXAMPLE 2 Preparation of 1-(2,4-Difluorophenyl-3-methylurea ##STR76##

Methyl isocyanate (9.6 g, 10 mL, 0.174 mol) is added to a solution of2,4-difluoroaniline (15 g, 0.116 mol) in toluene. The reaction mixtureis stirred for 1 hour and filtered to obtain a solid. The solid iswashed with hexanes and air-dried to give the title product as anoff-white solid, mp 182°-183° C.

Using essentially the same procedure, but using the appropriatelysubstituted aniline, the following compounds are obtained:

    ______________________________________                                         ##STR77##                                                                    U        X             Y     mp °C.                                    ______________________________________                                        NO.sub.2 H             F     229-232                                          H        F             Cl                                                     ______________________________________                                    

EXAMPLE 3 Preparation of1-(2-Chloro-4-fluorophenyl)-3-methyl-s-triazine-2,4,6(1H,3H,5H)-trione##STR78##

N-(Chlorocarbonyl) isocyanate (18.97 g, 0.180 mol) is added to a mixtureof 1-(2-chloro-4-fluorophenyl)-3-methylurea (29.2 g, 0.144 mol) intoluene. The reaction mixture is stirred for 90 minutes and filtered togive the title product as a white solid (32.1 g, mp 225°-228° C.).

Using essentially the same procedure, but using the appropriatelysubstituted urea, the following compounds are obtained:

    ______________________________________                                         ##STR79##                                                                    U        X             Y     mp °C.                                    ______________________________________                                        H        F             F     242-245                                          H        Cl            Cl    200-204                                          NO.sub.2 H             F     180-183                                          ______________________________________                                    

EXAMPLE 4 Preparation of1-(2-Chloro-4-fluoro-5-nitrophenyl)-3-methyl-s-triazine-2,4,6(1H,3H,5H)-trione##STR80##

Nitric acid (70% real, 8.3 mL, 0.131 mol) is added to a solution of1-(2-chloro-4-fluorophenyl)-3-methyl-s-triazine-2,4,6(1H,3H,5H)-trione(32.4 g, 0.119 mol) in concentrated sulfuric acid while maintaining thereaction mixture temperature below 10° C. After the addition iscomplete, the reaction mixture is stirred at room temperature for 30minutes, cooled to 10° C. and diluted with ice-water. The resultantaqueous mixture is filtered to obtain a solid which is washed with waterand air-dried to give the title product as a white solid (28.5 g, mp135°-139° C.).

Using essentially the same procedure, but using the appropriatelysubstituted 1-phenyl-3-methyl-s-triazine-2,4,6(1H,3H,5H)-trione, thefollowing compounds are obtained:

    ______________________________________                                         ##STR81##                                                                    X              Y     mp °C.                                            ______________________________________                                        F              F     100-120                                                  Cl             Cl    220-222                                                  ______________________________________                                    

EXAMPLE 5 Preparation of1-(5-Amino-2-chloro-4-fluorophenyl)-3-methyl-s-triazine-2,4,6(1H,3H,5H)-trione##STR82##

A mixture of1-(2-chloro-4-fluoro-5-nitrophenyl)-3-methyl-s-triazine-2,4,6(1H,3H,5H)-trione(28.5 g, 0.09 mol) and 5% platinum on activated carbon (1 g) in ethylacetate is hydrogenated at 55 psi until hydrogen uptake is complete. Thereaction mixture is then filtered and concentrated in vacuo to give thetitle product as a white solid, mp 244°-245° C.

Using essentially the same procedure, but using the appropriatelysubstituted 1-nitrophenyl-3-methyl-s-triazine-2,4,6(1H,3H,5H)-trione,the following compounds are obtained:

    ______________________________________                                         ##STR83##                                                                    X              Y     mp °C.                                            ______________________________________                                        F              F     194-196                                                  Cl             Cl    145-151                                                  H              F                                                              ______________________________________                                    

EXAMPLE 6 Preparation of1-[4-Chloro-2-fluoro-5-(hexahydro-3-methyl-2,4,6-trioxo-s-triazin-1-yl)phenyl]-1-cyclohexene-1,2-dicarboximide##STR84##

A mixture of1-(5-amino-2-chloro-4-fluorophenyl)-3-methyl-s-triazine-2,4,6(1H,3H,5H)-trione(23.4 g, 0.0816 mol) and 3,4,5,6-tetrahydrophthalic anhydride (13.04 g,0.0857 mol) in glacial acetic acid is stirred at 100° C. for 8 hours,cooled to 25° and poured into water. The resultant aqueous mixture isfiltered to obtain a solid which is washed with water and dried in avacuum oven to give the title product as a beige solid (22.5 g, mp154°-165° C.).

Using essentially the same procedure, but using the appropriatelysubstituted 1-(aminophenyl)-3-methyl-s-triazine-2,4,6(1H,3H,5H)-trione,the following compounds are obtained:

    ______________________________________                                         ##STR85##                                                                    X              Y     mp °C.                                            ______________________________________                                        F              F     135-150                                                  Cl             Cl    125-135                                                  H              F                                                              ______________________________________                                    

EXAMPLE 7 Preparation of Tert-butyl3-[2-chloro-5-(1-cyclohexene-1,2-dicarboximido)-4-fluorophenyl]tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR86##

A mixture of1-[4-chloro-2-fluoro-5-(hexahydro-3-methyl-2,4,6-trioxo-s-triazin-1-yl)phenyl]-1-cyclohexene-1,2-dicarboximide(8 g, 0.0199 mol) and potassium carbonate (4.13 g, 0.0299 mol) inN,N-dimethylformamide is treated with tert-butyl bromoacetate (5.82 g,0.0299 mol), stirred at room temperature for 18 hours and poured intowater. The resultant aqueous mixture is filtered to obtain a solid whichis washed with water and air-dried to give the title product as a whitesolid (6.13 g, mp 105°-115° C.).

Using essentially the same-procedure, but using the appropriatelysubstituted1-[5-(hexahydro-3-methyl-2,4,6-trioxo-s-triazin-1-yl)phenyl]-1-cyclohexene-1,2-dicarboximideand the appropriate alkylating agent, the following compounds areobtained:

    ______________________________________                                         ##STR87##                                                                    X     Y          R.sub.1      mp °C.                                   ______________________________________                                        F     F          CH.sub.2 CO.sub.2 CH.sub.3                                                                 100-115                                         F     Cl         CH.sub.2 CO.sub.2 CH.sub.3                                                                  95-110                                         Cl    Cl         CH.sub.2 CO.sub.2 C(CH.sub.3).sub.3                                                         95-100                                         Cl    Cl         CH.sub.2 CO.sub.2 CH.sub.3                                                                 120-125                                         H     F          CH.sub.2 CO.sub.2 CH.sub.3                                                                 110-120                                         F     Cl         CH.sub.2 CHCH.sub.2                                                                         91-106                                         F     Cl         CH.sub.2 CCH 105-122                                         ______________________________________                                    

EXAMPLE 8 Preparation of3-[2-Chloro-5-(1-cyclohexene-1,2-dicarboximido)-4-fluorophenyl]tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-aceticacid ##STR88##

A solution of tert-butyl3-[2-chloro-5-(1-cyclohexene-1,2-dicarboximido)-4-fluorophenyl]tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate(5.92 g, 0.011 mol) in trifluoroacetic acid is reluxed for 2 hours,cooled to room temperature and concentrated in vacuo to obtain an ambergum. The gum is dissolved in ether and the resultant solution isconcentrated in vacuo to give the title product as a yellow solid (3.62g, mp 75°-80° C.).

EXAMPLE 9 Preparation of Isopropyl3-[2-chloro-5-(1-cyclohexene-1,2-dicarboximido)-4-fluorophenyl]tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR89##

A solution of3-[2-chloro-5-(1-cyclohexene-1,2-dicarboximido)-4-fluorophenyl]tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-aceticacid (1.5 g, 3.13 mmol) in N,N-dimethylformamide is treated with2-iodopropane (0.849 g, 5 mmol) and potassium carbonate (0.69 g, 5mmol), stirred overnight at room temperature and poured into water. Theresultant aqueous mixture is filtered to obtain a solid which isair-dried to give the title product as a beige solid (0.6 g, mp100°-130° C.).

EXAMPLE 10 Preparation of N-[(4-Fluoro-3-nitrophenyl)carbamoyl]glycine,ethyl ester ##STR90##

A solution of 4-fluoro-3-nitrophenyl isocyanate (10 g, 0.055 mol) inanhydrous tetrahydrofuran is cooled to 0° C., treated with glycine ethylester hydrochloride (7.7 g, 0.055 mol), treated with triethylamine (5.56g, 0.055 mol) while maintaining the temperature below 10° C., stirred atroom temperature for 1 hour and poured into water. The aqueous mixtureis extracted with ether. The combined organic extracts are washedsequentially with 1N hydrochloric acid and brine, dried over anhydrousmagnesium sulfate, and concentrated in vacuo to obtain a solid which isair-dried to give the title product as a yellow solid (8.8 g, mp115°-120° C.).

EXAMPLE 11 Preparation of N-[(3-Amino-4-fluorophenyl)carbamoyl]glycine,ethyl ester ##STR91##

A mixture of N-[(4-fluoro-3-nitrophenyl)carbamoyl]glycine, ethyl ester(8 g, 0.029 mol) and 5% platinum on activated carbon (0.5 g) in ethylacetate is hydrogenated at 50 psi until hydrogen uptake is complete. Thereaction mixture is then filtered and cooled in an ice-bath until asolid forms. The solid is collected by filtration and airdried to givethe title product as a white solid (4.5 g, mp 152°-153° C.).

EXAMPLE 12 Preparation of{N-[3-(1-Cyclohexene-1,2-dicarboximido)-4-fluorophenyl]carbamoyl}glycine,ethyl ester ##STR92##

A solution of N-[(3-amino-4-fluorophenyl)carbamoyl]glycine, ethyl ester(4 g, 0.0157 mol) in acetic acid is treated with3,4,5,6-tetrahydrophthalic anhydride (2.43 g, 0.016 mol), heated at 100°C. for 8 hours, cooled to room temperature and poured into water. Theresultant aqueous mixture is filtered to obtain a solid which isrecrystallized from an ethyl acetate/hexanes solution to give the titleproduct as a yellow solid, mp 72°-82° C.

EXAMPLE 13 Preparation of Ethyl3-[3-(1-cyclohexene-1,2-dicarboximido)-4-fluorophenyl]tetrahydro-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR93##

A solution of{N-[3-(1-cylohexene-1,2-dicarboximido)-4-fluorophenyl]carbamoyl}glycine,ethyl ester (2.45 g, 6.3 mmol) in toluene is treated withN-(chlorocarbonyl) isocyanate (0.77 g, 7.3 mmol), stirred at 60° C. for12 hours and concentrated in vacuo to obtain a solid. The solid is driedin a vacuum oven at 85° C. for 24 hours to give the title product as ayellow solid (2.13 g, mp 135°-150° C.).

EXAMPLE 14 Preparation of5-[3-(1-Cyclohexene-1,2-dicarboximido)-4-fluorophenyl]dihydro-2,4,6-trioxo-s-triazine-1,3(2H,4H)-diaceticacid, 1-tert-butyl, ethyl ester ##STR94##

Tert-butyl bromoacetate (0.689 g, 3.5 mmol) and potassium carbonate(0.484 g, 3.5 mmol) are separately added to a solution of ethyl3-[3-(1-cyclohexene-1,2-dicarboximido)-4-fluorophenyl]tetrahydro-2,4,6-trioxo-s-triazine-1(2H)-acetate(1.35 g, 2.9 mmol) in N,N-dimethylformamide. The resultant reactionmixture is stirred at room temperature for 18 hours, poured into waterand extracted with ether. The organic extracts are combined, washed withbrine, dried over anhydrous magnesium sulfate and concentrated in vacuoto give the title product as an amber solid (0.8 g, mp 95°-105° C.).

EXAMPLE 15 Preparation of Isopropyl3-(2-chloro-4-fluorophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR95##

A mixture of1-(2-chloro-4-fluorophenyl)-3-methyl-s-triazine-2,4,6(1H,3H,5H)-trione(40.9 g, 0.150 mol), potassium carbonate (31.1 g, 0.225 mol) andisopropyl bromoacetate (29.1 mL, 0.225 mol) in N,N-dimethylformamide isstirred at room temperature for 2 hours, poured into water and extractedwith ethyl acetate. The organic extract is washed sequentially withwater and brine, dried over anhydrous magnesium sulfate and concentratedin vacuo to obtain an oil. Flash column chromatography of the oil usingsilica gel and 0% to 10% ether in methylene chloride solutions gives thetitle product as a white solid (51.5 g, mp 127°-128° C.).

EXAMPLE 16 Preparation of3-(2-Chloro-4-fluoro-5-nitrophenyl)tetrahydro-5-methlyl-2,4,6-trioxo-s-triazine-1(2H)-aceticacid ##STR96##

A solution of isopropyl3-(2-chloro-4-fluorophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate(48.7 g, 0.0508 mol) in concentrated sulfuric acid is cooled to 0° C.,treated with 90% nitric acid (2.6 mL), stirred at room temperatureovernight, treated with 90% nitric acid (1.0 mL), stirred for 4 hours,treated with nitric acid (2.0 mL), stirred at room temperatureovernight, treated with 90% nitric acid (1.0 mL), stirred for 1 hour andpoured onto ice. The resultant aqueous solution is filtered to obtain asolid. A solution of the solid in ether is dried over anhydrousmagnesium sulfate and concentrated in vacuo to give the title product asa yellow foam which is identified by NMR spectral analyses.

EXAMPLE 17 Preparation of Isopropyl3-(2-chloro-4-fluoro-5-nitrophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR97##

A solution of3-(2-chloro-4-fluoro-5-nitrophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-aceticacid (43.6 g, 0.105 mol) and concentrated sulfuric acid (25 mL) in2-propanol (300 mL) is refluxed for 12 hours, cooled to room temperatureand filtered to obtain a solid. The solid is dried to give the titleproduct as an off-white solid which is identified by NMR spectralanalyses. The filtrate is partially concentrated in vacuo and pouredover ice. The resultant aqueous mixture is extracted with ethyl acetateand the organic extract is dried over anhydrous magnesium sulfate andconcentrated in vacuo to obtain an orange oil. Flash columnchromatography of the oil using silica gel and 2.5% to 5% ether inmethylene chloride solutions gives additional title product as a yellowfoam.

EXAMPLE 18 Preparation of Isopropyl3-(5-amino-2-chloro-4-fluorophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR98##

A mixture of isopropyl3-(2-chloro-4-fluoro-5-nitrophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate(34.8 g, 0.0835 mol) and 5% platinum on carbon (3.48 g) in ethyl acetateis hydrogenated until about 90 psi of hydrogen is taken up. The reactionmixture is then filtered and concentrated in vacuo to obtain a foam.Column chromatography of the foam using silica gel and 10% to 20% etherin methylene chloride solutions gives a yellow foam which contains twocompounds. A mixture of the foam and 5% platinum on carbon (3.5 g) inethyl acetate is hydrogenated until 5 psi of hydrogen is taken up. Thereaction mixture is then filtered and concentrated in vacuo to give thetitle product as a yellow foam which is identified by NMR spectralanalyses.

EXAMPLE 19 Preparation of Isopropyl3-(2-chloro-4-fluoro-5-isocyanatophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR99##

A mixture of isopropyl3-(5-amino-2-chloro-4-fluorophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate(4.0 g, 0.0103 mol) in toluene is treated with a 1.93M solution ofphosgene in toluene (19 mL), refluxed for 3 hours, cooled, partiallyconcentrated in vacuo, diluted with toluene, partially concentrated invacuo, diluted with toluene and concentrated in vacuo to give the titleproduct as a yellow foam which is identified by ¹ H NMR spectralanalysis.

EXAMPLE 20 Preparation of Ethyl 3-thiomorpholinecarboxylate ##STR100##

A warm solution of 2-aminoethanethiol (10.0 g, 0.130 mol) andtriethylamine (36 mL, 0.260 mol) in chloroform is added over 5 minutesto a solution of ethyl 2,3-dibromopropionate (33.9 g, 0.130 mol) in achloroform/toluene (1:1.6) solution. The reaction mixture is stirred atroom temperature for 2.5 hours, filtered and concentrated in vacuo toobtain an orange liquid. The liquid is vacuum distilled to give thetitle product as a colorless liquid, bp 121°-124° C. at 3 mm Hg.

EXAMPLE 21 Preparation of Isopropyl3-{2-chloro-4-fluoro-5-[5,6,8,8a-tetrahydro-1,3-dioxo-1H-imidazo[5,1c][1,4]thiazin-2(3H)-yl]phenyl}tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR101##

A solution of isopropyl3-(2-chloro-4-fluoro-5-isocyanotophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate(3.11 g, 7.5 mmol) and ethyl 3-thiomorpholinecarboxylate (1.44 g, 8.2mmol) in toluene is stirred at room temperature for 1 hour, treated withseveral drops of ethyl 3-thiomorpholinecarboxylate, stirred at roomtemperature overnight and filtered to obtain a yellow solid. Theresultant filtrate is dried and concentrated in vacuo to obtain anorange foam. The solid and foam are combined and chromatographed usingsilica gel and a 10% ether in methylene chloride solution to obtain anorange foam containing two compounds. Flash column chromatography of thefoam using silica gel and a 15% ethyl acetate in methylene chloridesolution gives the title product as an off-white foam, mp 147°-155° C.

EXAMPLE 22 Preparation of Isopropyl3-[2-chloro-4-fluoro-5-(tetrahydro-1,3,7-trioxo-1H-imidazo[5,1-c][1,4]thiazin-2(3H)-yl)phenyl]tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR102##

A mixture of isopropyl3-{2-chloro-4-fluoro-5-[5,6,8,8a-tetrahydro-1,3-dioxo-1H-imidazo[5,1-c][1,4]thiazin-2(3H)-yl]phenyl}tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate(0.95 g, 1.75 mmol) in methanol (10 mL) is added over 15 minutes to asolution of sodium periodate (0.38 g, 1.78 mmol) in water (10 mL) whichis previously cooled to 0°-5° C. After the addition is complete, thereaction mixture is stirred at room temperature overnight, diluted withmethylene chloride, washed sequentially with a one molar KH₂ PO₄solution and brine, dried over anhydrous magnesium sulfate, andconcentrated in vacuo to obtain a yellow foam. Flash columnchromatography of the foam using silica gel, a 10% ether in methylenechloride solution and a 2.5% methanol in methylene chloride solutiongives the title product as a white foam (0.59 g, mp 175°-180° C.).

EXAMPLE 23 Preparation of Tetrahydro-1,2-pyridazinedicarboxylic acid,diethyl ester ##STR103##

1,4-Dibromobutane (81.4 mL, 0.682 mol) is added over 1 hour to a mixtureof 1,2-dicarbethoxyhydrazine (100 g, 0.568 mol) and potassium carbonate(158 g, 1.14 mol) in acetonitrile (600 mL). The resultant reactionmixture is refluxed for 6 hours, cooled to room temperature, andfiltered. The filtrate is concentrated in vacuo to obtain a yellowliquid which is distilled under reduced pressure to give the titleproduct as a colorless liquid (90.8 g, bp 115°-120° C. at 0.9 mm Hg).

EXAMPLE 24 Preparation of Hexahydropyridazine, hydrochloride ##STR104##

A solution of tetrahydro-1,2-pyridazinedicarboxylic acid, diethyl ester(45.0 g, 0.195 mol) in concentrated hydrochloric acid (190 mL) isrefluxed overnight, and concentrated in vacuo to obtain a white solid. Amixture of the solid in acetonitrile is stirred for one hour andfiltered to obtain a solid which is dried to give the title product as awhite solid (19.5 g, mp 163° C.).

EXAMPLE 25 Preparation of Isopropyl3-(2-chloro-4-fluoro-5-isothiocyanatophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR105##

Thiophosgene (0.50 mL, 6.5 mmol) is added over 45 minutes to a solutionof isopropyl3-(5-amino-2-chloro-4-fluorophenyl)tetrahydro-5-methyl-2,4,6-trioxo-S-triazine-1(2H)-acetate(2.5 g, 6.5 mmol), and triethylamine (1.8 mL, 13.0 mmol) intetrahydrofuran. The reaction mixture is stirred at room temperature for4 hours, diluted with tetrahydrofuran, and filtered. The filtrate isconcentrated in vacuo to give the title product as an orange oil whichis identified by NMR spectral analyses.

EXAMPLE 26 Preparation of Isopropyl3-{2-chloro-4-fluoro-5-[(tetrahydropyridazin-1(2H)-yl)thiocarboxamido]phenyl}tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR106##

Triethylamine (2.5 mL, 18.2 mmol) is added dropwise to a mixture ofisopropyl3-(2-chloro-4-fluoro-5-isothiocyanatophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate(2.79 g, 6.5 mmol), and hexahydropyridazine, hydrochloride (1.45 g, 9.1mmol) in methanol while maintaining the reaction mixture temperature at20°-25° C. After the addition is complete, the reaction mixture isstirred at room temperature overnight, partially concentrated in vacuo,and diluted with ethyl acetate. The organic phase is separated, washedsequentially with water and brine, dried over anhydrous magnesiumsulfate, and concentrated in vacuo to obtain an orange foam. Flashcolumn chromatography of the foam using silica gel and 2.5% to 10% etherin methylene chloride solutions gives the title product as a yellow foam(2.15 g, mp 105°-110° C.).

EXAMPLE 27 Preparation of Isopropyl3-{2-chloro-4-fluoro-5-[(tetrahydro-3-oxo-1H,3H-[1,3,4]thiadiazolo[3,4-a]pyridazin-1-ylidene)amino]phenyl}tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR107##

A solution of isopropyl3-{2-chloro-4-fluoro-5-(tetrahydropyridazin-1(2H)-yl)thiocarboxamido]phenyl}tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate(1.50 g, 2.9 mmol) in 1,2-dichloroethane is added over 30 minutes to a20% phosgene in toluene solution (2.91 mL, 5.6 mmol) which is previouslycooled to 0°-5° C. After the addition is complete, the reaction mixtureis stirred at room temperature for 2 hours, washed sequentially withwater and brine, dried over anhydrous magnesium sulfate, andconcentrated in vacuo to obtain a yellow foam. Flash columnchromatography of the foam using silica gel and 2.5% to 10% ether inmethylene chloride solutions gives the title product as a white foam(1.18 g, mp 97°-107° C.).

EXAMPLE 28 Preparation of 4'-Chloro-2'-fluoroacetanilide ##STR108##

Acetyl chloride (24.2 mL, 0.34 mol) is added slowly to a solution of4-chloro-2-fluoroaniline (49.4 g, 0.34 mol), and triethylamine (47 mL,0.34 mol) in tetrahydrofuran while maintaining the reaction mixturetemperature below 20° C. After the addition is complete, the reactionmixture is stirred overnight at room temperature, and poured into ethylacetate. The organic solution is washed sequentially with water andbrine, dried over anhydrous magnesium sulfate, and concentrated in vacuoto obtain an off-white solid. A mixture of the solid in ethanol isstirred for several minutes, and filtered to give the title product as awhite solid.

EXAMPLE 29 Preparation of 4'-Chloro-2'-fluoro-5'-nitroacetanilide##STR109##

A mixture of 4'-chloro-2'-fluoroacetanilide (51 g, 0.272 mol) inconcentrated sulfuric acid (100 mL) is cooled to 0° C., treated withnitric acid (90% real, 14 mL, 0.300 mol) over 45 minutes, stirred for 10minutes, and poured onto ice. The resultant aqueous mixture is filteredto obtain a tan solid which is washed with water, dried overnight, andrecrystallized from a chloroform/hexanes (17:1) solution to give thetitle product as a yellow solid.

EXAMPLE 30 Preparation of 5'-Amino-4'-chloro-2'-fluoroacetanilide##STR110##

A mixture of 4'-chloro-2'-fluoro-5'-nitroacetanilide (35.2 g, 151 mmol),and 5% platinum on carbon (7.0 g, 20 wt/wt %) in anethanol/tetrahydrofuran (2:1) solution is hydrogenated until 28 psi ofhydrogen is taken up. The reaction mixture is then filtered, andconcentrated in vacuo to give the title product as a tan solid which isidentified by ¹ H NMR spectral analysis.

EXAMPLE 31 Preparation of1-(5-Acetamido-2-chloro-4-fluorophenyl)-3-(2-propynyl)urea ##STR111##

A solution of 5'-amino-4'-chloro-2'-fluoroacetanilide (11.25 g, 55.6mmol), and triethylamine (7.70 mL, 55.6 mmol) in tetrahydrofuran isadded dropwise to a stirred solution of phenylchloroformate (8.70 mL,69.4 mmol) in tetrahydrofuran while maintaining the reaction mixturetemperature at 25°-30° C. After the addition is complete, the rectionmixture is stirred at room temperature for 75 minutes, and poured intoethyl acetate. The organic mixture is washed sequentially with water,saturated sodium hydrogen carbonate solution and brine, dried overanhydrous magnesium sulfate, and concentrated in vacuo to obtain a tansolid. A solution of the solid in tetrahydrofuran is treated withpropargylamine (9.52 mL, 139 mmol), refluxed for 1 hour, and poured intowater. The aqueous mixture is filtered to obtain a solid which is washedsequentially with water, 0.5N hydrochloric acid and water, and driedovernight to give the title product as a beige solid.

EXAMPLE 32 Preparation of4'-Chloro-2'-fluoro-5'-[hexahydro-2,4,6-trioxo-3-(2-propynyl)-s-triazin-1-yl]acetanilide##STR112##

A mixture of 1-(5-acetamido-2-chloro-4-fluorophenyl)-3-(2-propynyl)urea(4.50 g, 15.9 mmol), and pyridine (2.56 mL, 31.8 retool) in methylenechloride is treated with N-(chlorocarbonyl) isocyanate (1.92 mL, 23.9mmol), stirred at room temperature overnight, refluxed for 90 minutes,cooled to room temperature, treated with additional pyridine (1.30 mL)and N-(chlorocarbonyl) isocyanate (1.92 mL), stirred for 10 minutes,cooled to room temperature, and filtered to obtain a solid. The solid iswashed sequentially with water and hexanes, and dried to give the titleproduct as a tan solid.

EXAMPLE 33 Preparation of1-(5-Amino-2-chloro-4-fluorophenyl)-3-(2-propynyl)-s-triazine-2,4,6-(1H,3H,5H)-trione##STR113##

A mixture of4'-chloro-2'-fluoro-5'-[hexahydro-2,4,6-trioxo-3-(2-propynyl)-s-triazin-1-yl]acetanilide(3.00 g, 8.5 mmol), and 3N hydrochloric acid (25 mL) in ethanol (50 mL)is refluxed for 3 hours, cooled to room temperature, and poured intoethyl acetate. 3N sodium hydroxide solution (25 mL) is added to theorganic solution, and the phases are separated. The organic phase iswashed sequentially with saturated sodium hydrogen carbonate solutionand brine, and concentrated in vacuo to give the title product as abeige solid (2.17 g, mp 118°-121° C.).

EXAMPLE 34 Preparation ofN-{4-Chloro-2-fluoro-5-[hexahydro-2,4,6-trioxo-3-(2-propynyl)-s-triazin-1-yl]phenyl}-1-cyclohexene-1,2-dicarboximide##STR114##

A solution of1-(5-amino-2-chloro-4-fluorophenyl)-3-(2-propynyl)-s-triazine-2,4,6-(1H,3H,5H)-trione(1.50 g, 4.83 mmol), and 3,4,5,6-tetrahydrophthalic anhydride (0.73 g,4.83 mmol) in acetic acid (3 mL) is heated at 100° C. for 5 hours,cooled, and poured into ethyl acetate. The organic mixture is washedsequentially with water, saturated sodium hydrogen carbonate solutionand brine, dried over anhydrous magnesium sulfate, and concentrated invacuo to obtain a yellow semi-solid. Flash column chromatography of thesemi-solid using silica gel and an ethyl acetate/hexanes (1:2) solutiongives the title product as a white solid (1.20 g, mp 127°-135° C.).

EXAMPLE 35 Preparation ofN-(4-Chloro-2-fluorophenyl)-1-cyclohexene-1,2-dicarboximide ##STR115##

A mixture of 4-chloro-2-fluoroaniline (19.0 g, 130.6 mmol), and3,4,5,6-tetrahydrophthalic anhydride (19.85 g, 130.6 mmol) in aceticacid (150 mL) is refluxed for 2 hours, treated with additional4-chloro-2-fluoroaniline (3.0 g), refluxed for 90 minutes, stirred atroom temperature overnight and poured into a water/ethyl acetatemixture. The organic phase is washed sequentially with water, saturatedsodium hydrogen carbonate solution and brine, dried over anhydrousmagnesium sulfate and concentrated in vacuo to obtain a purple oil.Flash column chromatography of the oil using silica gel and 15% to 20%ethyl acetate in hexanes solutions gives the title product as anoff-white solid (25.3 g, mp 81°-82° C.).

EXAMPLE 36 Preparation ofN-(4-Chloro-2-fluoro-5-nitrophenyl)-1-cyclohexene-1,2-dicarboximide##STR116##

A mixture of N-(4-chloro-2-fluorophenyl)-1-cyclohexene-1,2-dicarboximide(24.4 g, 86.7 mmol) in sulfuric acid (150 mL) is cooled to -3° C.,treated dropwise with nitric acid (70% real, 6.70 mL, 104 mmol) whilemaintaining the temperature at 0°-2° C., stirred at room temperature for90 minutes, and poured onto ice. The aqueous mixture is stirred forseveral minutes, and filtered to obtain a solid which is washed withwater and dried to give the title product as a white powder (28.6 g, mp152°-155° C.).

EXAMPLE 37 Preparation ofN-(5-Amino-4-chloro-2-fluorophenyl)-1-cyclohexene-1,2-dicarboximide##STR117##

Iron powder (7.30 g, 130.7 mmol) is added portionwise to a mixture ofN-(4-chloro-2-fluoro-5-nitrophenyl)-1-cyclohexene-1,2-dicarboximide(10.6 g, 32.7 mmol) in acetic acid (100 mL) at 65° C. After the additionis complete, the reaction mixture is stirred for 10 minutes, andfiltered through diatomaceous earth. The filtrate is concentrated invacuo to obtain a dark solid. A mixture of the solid in an ethylacetate/saturated sodium hydrogen carbonate solution is filtered throughdiatomaceous earth, and the phases are separated. The organic phase iswashed sequentially with saturated sodium hydrogen carbonate solutionand brine, dried over anhydrous magnesium sulfate, and concentrated invacuo to give the title product as a yellow solid.

EXAMPLE 38 Preparation of1-Allyl-3-[2-chloro-5-(1-cyclohexene-2-dicarboximido)-4-fluorophenyl]urea##STR118##

A mixture ofN-(5-amino-4-chloro-2-fluorophenyl)-1-cyclohexene-1,2-dicarboximide(3.50 g, 11.9 mmol) in toluene (25 mL) is treated with allyl isocyanate(2.10 mL, 23.8 mmol), heated at 60° C. for 21 hours, treated withadditional allyl isocyanate (0.53 mL), heated at 60° C. for hours,cooled to 20°-30° C., and filtered to obtain a solid which is washedwith hexanes to give the title product as a tan solid (3.15 g, mp 236°14238° C.).

EXAMPLE 39 Preparation ofN-[5-(3-Allylhexahydro-2,4,6-trioxo-s-triazin-1-yl)-4-chloro-2-fluorophenyl]-1-cyclohexene-1,2-dicarboximide##STR119##

A mixture of1-allyl-3-[2-chloro-5-(1-cyclohexene-1,2-dicarboximido)-4-fluorophenyl]urea(2.34 g, 6.21 mmol) in toluene (25 mL) is treated withN-(chlorocarbonyl) isocyanate (0.75 mL, 9.31 mmol), stirred at 60° C.for 3 hours, cooled to room temperature, and concentrated in vacuo toobtain an oil. Flash column chromatography of the oil using silica geland an ethyl acetate/hexanes (2:3) solution gives the title product as awhite solid (2.6 g, mp 130°-145° C.).

EXAMPLE 40 Preparation ofN-{5-[3-Allylhexahydro-2,4,6-trioxo-5-(2-propynyl)-s-triazin-1-yl]-4-chloro-2-fluorophenyl}-1-cyclohexene-1,2-dicarboximide##STR120##

Propargyl bromide (0.37 mL, 3.36 mmol) is added to a mixture ofN-[5-(3-allylhexahydro-2,4,6-trioxo-s-triazin-1-yl)-4-chloro-2-fluorophenyl]-1-cyclohexene-1,2-dicarboximide(1.00 g, 2.24 mmol), and potassium carbonate (0.62 g, 4.48 mmol) inN,N-dimethylformamide. The reaction mixture is stirred for 7 hours, andpoured into ethyl acetate. The organic solution is washed sequentiallywith water and brine, dried over anhydrous magnesium sulfate, andconcentrated in vacuo to obtain a yellow oil. Flash columnchromatography of the oil using silica gel and an ethyl acetate/hexanes(1:4) solution gives the title product as a white solid (0.60 g, mp107°-114° C.).

Using essentially the same procedure, but substituting allyl bromide forpropargyl bromide,N-[4-chloro-5-(3,5-diallylhexahydro-2,4,6-trioxo-s-triazin-1-yl)-2-fluorophenyl]-1-cyclohexene-1,2-dicarboximideis obtained as a white solid, mp 80°-85° C.

EXAMPLE 41 Preparation of Isopropyl3-[2-chloro-4-fluoro-5-(3-fluorophthalimido)phenyl]tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate##STR121##

A solution of isopropyl3-(5-amino-2-chloro-4-fluorophenyl)tetrahydro-5-methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate(1.0 g, 2.6 mmol) and 3-fluorophthalic anhydride (0.51 g, 3.1 mmol) inacetic acid is refluxed for 6 hours, stirred at room temperature forseveral days and poured onto ice. The resultant aqueous mixture isfiltered to obtain a solid. The solid is dried and chromatographed(silica gel/2.5% ether in methylene chloride solution) to give the titleproduct as a yellow foam, mp 119°-125° C.

EXAMPLE 42 Postemergence herbicidal evaluation of test compounds

The postemergence herbicidal activity of the compounds of the presentinvention is demonstrated by the following tests, wherein a variety ofdicotyledonous and monocotyledonous plants are treated with testcompounds, dispersed in aqueous acetone mixtures. In the tests, seedlingplants are grown in jiffy flats for about two weeks. The test compoundsare dispersed in 50/50 acetone/water mixtures containing 0.5% TWEEN® 20,a polyoxyethylene sorbitan monolaurate surfactant of Atlas ChemicalIndustries, in sufficient quantities to provide the equivalent of about0.125 kg to 0.500 kg per hectare of active compound when applied to theplants through a spray nozzle operating at 40 psi for a predeterminedtime. After spraying, the plants are placed on greenhouse benches andare cared for in the usual manner, commensurate with conventionalgreenhouse practices. From four to five weeks after treatment, theseedling plants are examined and rated according to the rating systemset forth below. Data obtained are reported in Table I below. Where morethan one test is involved for a given compound, the data are averaged.

Plant species employed in these evaluations are reported by headerabbreviation, common name and scientific name.

Compounds employed in this postemergence herbicidal evaluation and inthe preemergence evaluation in the following example are given acompound number and identified by name. Data in Table I are reported bycompound number.

Herbicide Rating Scale

Results of herbicide evaluation are expressed on a rating scale (0-9).The scale is based upon a visual observation of plant stand, vigor,malformation, size, chlorosis and overall plant appearance as comparedwith a control.

    ______________________________________                                                                  % Control                                           Rating Meaning            Compared to Check                                   ______________________________________                                        9      Complete kill      100                                                 8      Approaching Complete Kill                                                                        91-99                                               7      Good Herbicidal Effect                                                                           80-90                                               6      Herbicidal Effect  65-79                                               5      Definite Injury    45-64                                               4      Injury             30-44                                               3      Moderate Effect    16-29                                               2      Slight Effect       6-15                                               1      Trace Effect       1-5                                                 0      No Effect          0                                                   --     No Evaluation                                                          ______________________________________                                    

    ______________________________________                                        PLANT SPECIES                                                                 EMPLOYED IN HERBICIDAL EVALUATIONS                                            Header                                                                        Abb.    Common Name Scientific Name                                           ______________________________________                                        ABUTH   Velvetleaf  ABUTILON THEOPHRASTI,                                                         MEDIC.                                                    AMBEL   Ragweed,    AMBROSIA ARTEMISII-                                               Common      FOLIA, L.                                                 CASOB   Sicklepod   CASSIA OBTUSIFOLIA, L.                                    CHEAL   Lambsquarters,                                                                            CHENOPODIUM ALBUM, L.                                             Common                                                                IPOSS   Morningglory                                                                              IPOMOEA SPP.                                                      Spp.                                                                  GALAP   Galium      GALIUM APARINE                                            ECHCG   Barnyardgrass                                                                             ECHINOCHLOA CRUS-GALLI,                                                       (L) BEAU                                                  SETVI   Foxtail,    SETARIA VIRIDIS,                                                  Green       (L) BEAU                                                  GLXMAW  Soybean,    GLYCINE MAX(L)MERR. CV.                                           Williams    WILLIAMS                                                  ORYSAT  Rice,       ORYZA SATIVA, L.                                                  Tebonnet    TEBONNET                                                  TRZAWO  Wheat, Winter,                                                                            TRITICUM                                                          CV. APOLLO  AESTIVUM, CV. APOLLO                                      ZEAMX   Corn, Field ZEA MAYS L.                                               ______________________________________                                    

    ______________________________________                                        COMPOUNDS EVALUATED                                                           AS HERBICIDAL AGENTS                                                          Compound                                                                      Number                                                                        ______________________________________                                        1         Methyl 3-[2-Chloro-5-(1-cyclohexene-1,2-                                      dicarboximido)-4-fluorophenyl]tetrahydro-5-                                   methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate                        2         Tert-butyl 3-[2-chloro-5-(1-cyclohexene-1,2-                                  dicarboximido)-4-fluorophenyl]tetrahydro-5-                                   methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate                        3         3-[2-Chloro-5-(1-cyclohexene-1,2-dicarbox-                                    imido)-4-fluorophenyl]tetrahydro-5-methyl-                                    2,4,6-trioxo-s-triazine-1(2H)-acetic acid                           4         Isopropyl 3-[2-chloro-5-(1-cyclohexene-1,2-                                   dicarboximido)-4-fluorophenyl]tetrahydro-5-                                   methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate                        5         Methyl 3-[5-(1-cyclohexene-1,2-dicarbox-                                      imido)-2-fluorophenyl]tetrahydro-5-methyl-                                    2,4,6-trioxo-s-triazine-1(2H)-acetate                               6         Methyl 3-[2,4-dichloro-5-(1-cyclohexene-1,2-                                  dicarboximido)phenyl]tetrahydro-5-methyl-                                     2,4,6-trioxo-s-triazine-1(2H)-acetate                               7         Tert-butyl 3-[2,4-dichloro-5-(1-cyclohexene-                                  1,2-dicarboximido)phenyl]tetrahydro-5-                                        methyl-2,4,6-trioxo-s-triazine-1(2H)-acetate                        8         5-[3-(1-Cyclohexene-1,2-dicarboximido)-4-                                     fluorophenyl]dihydro-2,4,6-trioxo-s-tri-                                      azine-1,3(2H,4H)-diacetic acid, 1-tert-                                       butyl, ethyl ester                                                  9         Ethyl 3-[3-(1-cyclohexene-1,2-dicarbox-                                       imido)-4-fluorophenyl]tetrahydro-2,4,6-                                       trioxo-s-triazine-1(2H)-acetate                                     10        Methyl 3-[5-(1-cyclohexene-1,2-dicarbox-                                      imido)-2,4-difluorophenyl]-5-methyl-2,4,6-                                    trioxo-s-triazine-1(2H)-acetate                                     11        Isopropyl 3-[2-chloro-4-fluoro-5-(3-fluoro-                                   phthalimido)phenyl]tetrahydro-5-methyl-                                       2,4,6-trioxo-s-triazine-1(2H)-acetate                               12        Isopropyl 3-{2-chloro-4-fluoro-5-[5,6,8,8a-                                   tetrahydro-1,3-dioxo-1H-imidazo[5,1c][1,4]-                                   thiazin-2(3H)-yl]phenyl}tetrahydro-5-methyl-                                  2,4,6-trioxo-s-triazine-1(2H)-acetate                               13        Isopropyl 3-{2-chloro-4-fluoro-5-[(tetra-                                     hydro-3-oxo-1H,3H-[1,3,4]thiadiazolo[3,4-                                     a]pyridazin-1-ylidene)amino]phenyl}tetra-                                     hydro-5-methyl-2,4,6-trioxo-s-triazine-                                       1(2H)-acetate                                                       14        Isopropyl 3-[2-chloro-4-fluoro-5-(tetra-                                      hydro-1,3,7-trioxo-1H-imidazo[5,1-c][1,4]-                                    thiazin-2(3H)-yl)phenyl]tetrahydro-5-methyl-                                  2,4,6-trioxo-s-triazine-1(2H)-acetate                               15        N-{4-Chloro-2-fluoro-5-[hexahydro-2,4,6-                                      trioxo-3-(2-propynyl)-s-triazin-1-yl]-                                        phenyl}-1-cyclohexene-1,2-dicarboximide                             16        N-{4-Chloro-2-fluoro-5-[hexahydro-3-methyl-                                   2,4,6-trioxo-5-(2-propynyl)-s-triazin-1-                                      yl]phenyl}-1-cyclohexene-1,2-dicarboximide                          17        N-[5-(3-Allylhexahydro-5-methyl-2,4,6-                                        trioxo-s-triazin-1-yl)-4-chloro-2-fluoro-                                     phenyl]-1-cyclohexene-1,2-dicarboximide                             18        N-[5-(3-Allylhexahydro-2,4,6-trioxo-s-                                        triazin-1-yl)-4-chloro-2-fluorophenyl]-1-                                     cyclohexene-1,2-dicarboximide                                       19        N-[4-Chloro-5-(3,5-diallylhexahydro-2,4,6-                                    trioxo-s-triazin-1-yl)-2-fluorophenyl]-1-                                     cyclohexene-1,2-dicarboximide                                       20        N-{5-[3-Allylhexahydro-2,4,6-trioxo-5-(2-                                     propynyl)-s-triazin-1-yl]-4-chloro-2-fluoro-                                  phenyl}-1-cyclohexene-1,2-dicarboximide                             ______________________________________                                    

    TABLE I      - Postemergence Herbicidal Evaluations of Test Compounds      Compound Rate      Number (kg/ha) ABUTH AMBEL CASOB CHEAL IPOSS GALAP ECHCG SETVI GLXMAW     ORYSAT TRZAWO ZEAMX      1 0.500 9.0 9.0 7.0 4.0 8.0 4.0 1.0 2.0 7.0 4.5 5.5 5.0       0.250 9.0 9.0 7.0 3.0 9.0 3.0 0.0 0.0 6.5 4.5 5.5 4.5       0.125 9.0 7.0 5.0 2.0 8.0 3.0 0.0 0.0 5.0 3.5 4.0 4.5      2 0.500 9.0 8.5 7.0 8.0 7.0 8.5 0.5 0.5 5.5 4.5 4.5 4.3       0.250 9.0 7.5 5.5 7.5 8.0 9.0 0.0 0.0 5.5 3.8 4.3 4.0       0.125 9.0 6.0 5.0 5.5 7.5 7.0 0.0 0.0 4.3 3.0 3.5 3.3      3 0.500 2.0 3.0 3.0 2.0 5.0 2.0 0.0 0.0 4.0 4.0 5.0 4.5       0.250 0.0 3.0 2.0 2.0 4.0 2.0 0.0 0.0 4.5 4.0 4.5 4.5       0.125 1.0 1.0 2.0 0.0 2.0 0.0 0.0 0.0 3.5 3.0 4.0 4.0      4 0.500 9.0 9.0 9.0 8.0 8.0 8.0 2.0 3.0 7.0 4.0 5.0 4.5       0.250 9.0 7.0 8.0 8.0 8.0 7.0 0.0 1.0 6.0 4.0 4.5 4.5       0.125 9.0 5.0 7.0 6.0 7.0 6.0 0.0 0.0 5.0 4.0 4.5 4.5      5 0.500 2.0 2.0 0.0 0.0 5.0 3.0 0.0 2.0 4.5 2.0 2.0 3.5       0.250 0.0 2.0 0.0 0.0 2.0 2.0 0.0 0.0 4.5 2.0 1.0 2.5       0.125 2.0 2.0 0.0 0.0 3.0 0.0 0.0 0.0 4.0 1.5 1.0 2.5      6 0.500 8.0 5.0 4.5 7.5 7.0 4.5 1.0 2.0 5.0 2.8 3.5 3.8       0.250 6.5 4.5 4.5 8.0 6.0 4.0 1.0 1.0 4.3 2.8 3.3 3.8       0.125 6.0 3.5 3.0 5.5 5.5 3.0 0.0 0.0 4.0 2.0 2.5 3.0      7 0.500 7.5 7.5 6.0 8.0 7.0 6.0 1.0 1.0 5.0 3.0 3.3 4.8       0.250 9.0 7.5 6.0 8.0 6.0 4.5 1.0 1.0 5.0 3.0 2.5 4.8       0.125 7.0 6.0 5.0 7.0 5.5 2.5 0.0 0.0 4.5 2.3 2.5 3.8      8 0.500 3.0 3.0 0.0 2.0 3.0 4.0 0.0 0.0 2.0 1.5 0.5 0.5       0.250 3.0 2.0 0.0 2.0 2.0 4.0 0.0 0.0 2.5 1.5 0.5 0.5       0.125 2.0 0.0 0.0 0.0 3.0 2.0 0.0 0.0 1.5 1.5 0.5 0.0      9 0.500 5.4 2.0 0.0 2.0 4.0 3.0 0.0 0.0 3.5 2.0 2.0 1.5       0.250 4.0 2.0 0.0 0.0 2.0 2.0 0.0 0.0 2.5 2.0 2.0 1.5       0.125 3.0 0.0 0.0 0.0 2.0 2.0 0.0 0.0 2.0 1.5 1.0 1.0      10 0.500 9.0 6.0 0.0 0.0 5.0 0.0 0.0 0.0 4.5 4.0 4.0 4.0       0.250 6.0 4.0 2.0 2.0 4.0 2.0 0.0 0.0 4.0 3.5 3.5 4.0       0.125 6.0 4.0 1.0 0.0 8.0 0.0 0.0 0.0 3.5 3.0 3.5 4.0      11 0.500 7.0 9.0 6.0 9.0 6.0 3.0 3.0 3.0 5.5 2.0 1.0 3.0       0.250 6.0 6.0 4.0 9.0 4.0 2.0 3.0 3.0 4.5 2.0 0.5 2.5       0.125 9.0 9.0 4.0 9.0 3.0 1.0 3.0 2.0 4.0 1.5 0.5 2.5      12 0.500 9.0 9.0 9.0 9.0 9.0 8.0 3.0 4.0 6.5 3.0 2.5 5.0       0.250 9.0 9.0 9.0 9.0 9.0 8.0 3.0 3.0 5.5 3.5 2.5 4.5       0.125 9.0 9.0 9.0 9.0 7.0 7.0 2.0 2.0 6.5 3.0 2.5 4.0      13 0.500 9.0 9.0 9.0 9.0 9.0 8.0 0.0 1.0 6.5 4.0 3.5 4.0       0.250 9.0 7.0 9.0 9.0 8.0 9.0 0.0 1.0 5.5 4.5 3.5 3.5       0.125 9.0 6.0 7.0 8.0 7.0 7.0 0.0 1.0 5.5 4.0 3.5 3.5      14 0.500 6.0 6.0 5.0 7.0 4.0 4.0 0.0 1.0 4.5 4.5 2.0 1.5       0.250 5.0 5.0 5.0 8.0 3.0 4.0 0.0 1.0 4.0 2.5 2.0 1.0       0.125 3.0 4.0 5.0 6.0 3.0 3.0 0.0 1.0 3.5 2.5 2.0 1.5      15 0.500 2.0 5.0 1.0 9.0 2.0 9.0 4.0 5.0 6.0 2.0 5.0 6.0       0.250 0.0 5.0 0.0 8.0 0.0 5.0 3.0 4.0 4.0 0.0 3.0 5.0       0.125 0.0 3.0 0.0 8.0 0.0 5.0 3.0 4.0 2.0 0.0 2.0 3.0      16 0.500 4.0 4.0 3.0 5.0 6.0 4.0 0.0 0.0 4.0 4.5 4.0 4.0       0.250 3.0 4.0 2.0 5.0 6.0 4.0 0.0 0.0 3.5 4.5 3.5 3.5       0.125 2.0 2.0 1.0 4.0 4.0 3.0 0.0 0.0 3.0 3.0 2.5 2.5      17 0.500 8.0 7.0 2.0 8.0 5.0 4.0 0.0 2.0 5.5 3.5 3.0 4.0       0.250 6.0 5.0 3.0 6.0 3.0 3.0 0.0 1.0 4.0 2.5 2.5 3.0       0.125 6.0 4.0 2.0 5.0 3.0 2.0 0.0 1.0 3.0 2.5 2.0 2.5      18 0.500 6.0 5.0 4.0 7.0 4.0 6.0 4.0 4.0 5.5 4.0 4.5 5.0       0.250 1.0 3.0 3.0 7.0 2.0 2.0 0.0 2.0 3.5 3.0 3.5 3.5       0.125 0.0 1.0 2.0 6.0 2.0 0.0 0.0 1.0 4.0 2.0 2.5 2.0      19 0.500 3.0 6.0 2.0 7.0 3.0 4.0 0.0 0.0 1.0 2.0 2.0 3.0       0.250 3.0 5.0 0.0 6.0 3.0 4.0 0.0 0.0 1.0 2.0 2.0 2.0       0.125 1.0 4.0 0.0 4.0 1.0 3.0 0.0 0.0 1.0 2.0 2.0 1.0      20 0.500 6.0 6.0 2.0 8.0 6.0 8.0 0.0 0.0 2.0 2.0 2.0 3.0       0.250 6.0 5.0 0.0 7.0 4.0 2.0 0.0 0.0 1.0 2.0 2.0 2.0       0.125 3.0 4.0 0.0 7.0 2.0 2.0 0.0 0.0 1.0 2.0 1.0 2.0

EXAMPLE 43 Preemergence herbicidal evaluation of test compounds

The preemergence herbicidal activity of the test compounds of thepresent invention is exemplified by the following tests in which theseeds of a variety of monocotyledonous and dicotyledonous plants areseparately mixed with potting soil and planted on top of approximatelyone inch of soil in separate pint cups. After planting, the cups aresprayed with the selected aqueous acetone solution containing testcompound in sufficient quantity to provide the equivalent of about 0.125to 0.50 kg per hectare of test compound per cup. The treated cups arethen placed on greenhouse benches, watered and cared for in accordancewith conventional greenhouse procedures. From four to five weeks aftertreatment, the tests are terminated and each cup is examined and ratedaccording to the rating system provided in Example 42.

The data obtained are reported in Table II below. The compoundsevaluated are reported by compound number given in Example 42.

    TABLE II      - Preemergence Herbicidal Evaluations of Test Compounds      Compound Rate      Number (kg/ha) ABUTH AMBEL CASOB CHEAL IPOSS GALAP ECHCG SETVI GLXMAW     ORYSAT TRZAWO ZEAMX      1 0.500 8.0 4.0 6.0 9.0 0.0 0.0 3.0 4.0 0.0 0.0 0.0 0.0       0.250 9.0 0.0 5.0 9.0 2.0 0.0 0.0 2.0 0.0 0.0 0.0 0.0       0.125 0.0 0.0 5.0 9.0 0.0 -- 0.0 2.0 0.0 0.0 0.0 0.0      2 0.500 9.0 7.0 8.0 9.0 6.0 6.0 0.0 0.0 0.0 1.0 1.0 2.0       0.250 9.0 5.0 3.0 9.0 6.0 9.0 0.0 0.0 0.0 1.0 1.0 0.0       0.125 7.0 5.0 4.0 9.0 6.0 7.0 0.0 0.0 0.0 0.0 1.0 0.0      3 0.500 0.0 0.0 6.0 7.0 0.0 3.0 2.0 4.0 0.0 0.0 0.0 0.0       0.250 0.0 0.0 4.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0       0.125 0.0 0.0 3.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0      4 0.500 9.0 6.0 9.0 9.0 6.0 9.0 0.0 4.0 0.0 2.0 4.0 3.0       0.250 9.0 3.0 0.0 9.0 3.0 9.0 0.0 2.0 0.0 1.0 2.0 3.0       0.125 6.0 2.0 0.0 9.0 2.0 9.0 0.0 0.0 0.0 1.0 2.0 0.0      5 0.500 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0       0.250 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0       0.125 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0      6 0.500 4.0 3.0 5.0 9.0 4.0 9.0 0.0 2.0 1.0 4.0 2.0 1.0       0.250 4.0 3.0 3.0 9.0 4.0 3.0 0.0 0.0 1.0 4.0 2.0 0.0       0.125 3.0 2.0 2.0 6.0 4.0 -- 0.0 0.0 0.0 4.0 2.0 1.0      7 0.500 3.0 -- 0.0 8.0 0.0 5.0 0.0 0.0 0.0 5.0 2.0 0.0       0.250 2.0 0.0 0.0 8.0 0.0 3.0 0.0 0.0 0.0 3.0 1.0 0.0       0.125 0.0 0.0 0.0 5.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0 0.0      8 0.500 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0       0.250 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0       0.125 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0      9 0.500 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0       0.250 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0       0.125 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0      10 0.500 0.0 0.0 6.0 8.0 0.0 4.0 3.0 3.0 0.0 0.0 0.0 0.0       0.250 0.0 0.0 6.0 9.0 0.0 3.0 0.0 4.0 0.0 2.0 0.0 0.0       0.125 -- 0.0 4.0 3.0 0.0 -- 0.0 1.0 0.0 2.0 0.0 0.0      11 0.500 3.0 0.0 0.0 9.0 0.0 -- 0.0 0.0 0.0 0.0 0.0 0.0       0.250 3.0 0.0 0.0 9.0 0.0 -- 0.0 0.0 0.0 0.0 0.0 0.0       0.125 0.0 0.0 0.0 9.0 0.0 -- 0.0 0.0 0.0 0.0 0.0 0.0      12 0.500 9.0 3.0 9.0 9.0 4.0 -- 0.0 3.0 1.0 0.0 0.0 3.0       0.250 9.0 0.0 9.0 9.0 6.0 -- 0.0 0.0 1.0 0.0 0.0 1.0       0.125 5.0 0.0 9.0 9.0 2.0 -- 0.0 0.0 0.0 0.0 0.0 0.0      13 0.500 9.0 8.0 9.0 9.0 6.0 9.0 0.0 7.0 0.0 2.0 1.0 1.0       0.250 9.0 3.0 9.0 9.0 5.0 8.0 0.0 7.0 0.0 1.0 0.0 0.0       0.125 9.0 0.0 5.0 9.0 2.0 9.0 0.0 0.0 0.0 0.0 0.0 0.0      14 0.500 4.0 3.0 4.0 9.0 3.0 9.0 0.0 1.0 0.0 4.0 2.0 1.0       0.250 0.0 2.0 2.0 6.0 1.0 7.0 0.0 0.0 0.0 2.0 1.0 0.0       0.125 0.0 0.0 2.0 7.0 0.0 7.0 0.0 0.0 0.0 0.0 0.0 0.0      16 0.500 9.0 2.0 0.0 9.0 0.0 4.0 0.0 3.0 0.0 0.0 0.0 2.0       0.250 6.0 0.0 0.0 8.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0       0.125 2.0 0.0 0.0 6.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0      17 0.500 9.0 2.0 0.0 9.0 0.0 4.0 0.0 3.0 0.0 2.0 0.0 3.0       0.250 3.0 0.0 0.0 9.0 0.0 7.0 0.0 0.0 0.0 0.0 0.0 0.0       0.125 0.0 0.0 0.0 6.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0      18 0.500 0.0 0.0 0.0 7.0 4.0 4.0 0.0 0.0 0.0 0.0 0.0 0.0       0.250 0.0 0.0 0.0 5.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0       0.125 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

What is claimed is:
 1. A process for the preparation of a compoundhaving the structural formula ##STR122## wherein X and Y are eachindependently hydrogen, halogen, nitro, cyano, C₁ -C₄ alkyl, C₁ -C₄haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy or S(O)_(m) R₂ ;m is aninteger of 0, 1 or 2; R₂ is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl; R ishydrogen, C₁ -C₆ alkyl, C₂ -C₁₂ alkoxyalkyl, C₃ -C₁₂ alkylcarbonylalkyl,C₃ -C₁₂ haloalkylcarbonylalkyl, C₃ -C₁₂ alkoxycarbonylalkyl, C₃ -C₁₂haloalkoxycarbonylalkyl, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl,phenyloptionally substituted with one to three halogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy or C₁ -C₄ haloalkoxy groups, or benzyl optionally substitutedwith one to three halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄haloalkoxy groups; R₁ is hydrogen, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl,cyano,C₁ -C₁₂ alkyl optionally substituted with one or more halogenatoms, or one cyano, C(O)R₃, OC(O)R₅, CH₂ OC(O)R₅, OR₄, CH₂ OR₄ or CR₆(OR₇)₂ group, or one phenyl group optionally substituted with one tothree halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄ -haloalkoxy groups,or phenyl optionally substituted with one to three halogen, C₁ -C₄alkyl, C₁ -C₄ alkoxy or C₁ -C₄ -haloalkoxy groups; R₃ is OR₈, SR₈ or NR₉R₁₀ ; R₄, R₅ and R₆ are each independently hydrogen, C₁ -C₄ alkyl or C₁-C₄ haloalkyl; R₇ is C₁ -C₄ alkyl; R₈ is C₁ -C₆ alkyl optionallysubstituted with C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, halogen, hydroxy, C₃-C₆ cycloalkyl, furyl or phenyl optionally substituted with one or morehalogen, cyano, nitro, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy orC₁ -C₄ haloalkoxy groups,C₃ -C₆ alkenyl optionally substituted with C₁-C₄ alkoxy, halogen, C₃ -C₆ cycloalkyl or phenyl optionally substitutedwith one or more halogen, cyano, nitro, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl,C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups, C₃ -C₆ alkynyl optionallysubstituted with C₁ -C₄ alkoxy or halogen, or C₃ -C₆ cycloalkyl; R₉ andR₁₀ are each independently hydrogen,C₁ -C₆ alkyl, benzyl optionallysubstituted with one or more halogen, cyano, nitro, C₁ -C₄ alkyl, C₁ -C₄haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups, or phenyloptionally substituted with one or more halogen, cyano, nitro, C₁ -C₄alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkoxy groups; R₁₁and R₁₂ are each independently hydrogen,C₁ -C₆ alkyl optionallysubstituted with one or more halogen atoms, or C₃ -C₆ cycloalkyloptionally substituted with one or more halogen atoms, and when R₁₁ andR₁₂ are taken together with the atoms to which they are attached, theyrepresent a four- to seven-membered saturated or unsatureated ringoptionally interrupted by O, S(O)_(r) or N, and optionally substitutedwith one to three methyl groups or one or more halogen atoms; A, A₁, A₂,A₃ and A₄ are each independently O or S; r is an integer of 0, 1 or 2;and Z is N or CH, which comprises reacting an isocyanate orisothiocyanate having the structural formula ##STR123## wherein X, Y, R,R₁, A, A₁, A₂ and A₃ are as described above with a hydrazine having thestructural formula ##STR124## wherein R₁₁, R₁₂, Z and A₄ are asdescribed above and R₂₂ is C₁ -C₄ alkyl to form an intermediatecompound, and cyclizing the intermediate compound with base.
 2. Theprocess according to claim 1 whereinX is hydrogen or halogen; Y ishydrogen, halogen, nitro or cyano; R is hydrogen, C₁ -C₄ alkyl, C₁ -C₄alkoxymethyl, (C₁ -C₄ alkoxy)carbonylmethyl, C₃ -C₆ alkenyl or C₃ -C₆alkynyl; R₁ is hydrogen, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl or C₁ -C₆ alkyloptionally substituted with one CO₂ R₈ group; R₈ is C₁ -C₆ alkyl; R₁₁and R₁₂ are taken together with the atoms to which they are attached toform a ring in which R₁₁ R₁₂ is a C₂ -C₅ alkylene group optionallyinterrupted by S(O)_(r), and optionally substituted with one to threemethyl groups or one or more halogen atoms, or R₁₁ R₁₂ is represented bythe structure: --CR₁₈ ═CR₁₉ --CR₂₀ ═CR₂₁ -- where R₁₈, R₁₉, R₂₀ and R₂₁are each independently hydrogen, halogen or methyl; A, A₁, A₂, A₃ and A₄are O; and r is an integer of 0, 1 or 2.